Epoxy compound, composition prepared therefrom, semiconductor device prepared therefrom, electronic device prepared therefrom, article prepared therefrom, and method of preparing epoxy compound

ABSTRACT

An epoxy compound having an aromatic ring represented by Formula 1 or Formula 2, a composition prepared from the epoxy compound, a semiconductor device prepared from the epoxy compound, an electronic device prepared from the epoxy compound, an article prepared from the epoxy compound, and a method of preparing the epoxy compound: 
       E1-(M1) a1 -(L1) b1 -(M2) a2 -L2-A1-L3-(M3) a3 -(L4) b2 -(M4) a4 -E2  Formula 1
 
       E3-(A2) c1 -(L5) b3 -(M5) a5 -L6-(M6) a6 -L7-(M7) a7 -(L8) b4 -(A3) c2 -E4  Formula 2
 
     In Formulae 1 and 2, M1, M2, M3, M4, M5, M6, M7, A1, A2, A3, L1, L2, L3, L4, L5, L6, L7, L8, E1, E2, E3, E4, a1, a2, a3, a4, a5, a6, a7, b1, b2, b3, b4, c1, and c2 are the same as defined in the detailed description.

CROSS-REFERENCE TO RELATED APPLICATION

This application is based on and claims priority to Korean PatentApplication No. 10-2020-0175827, filed on Dec. 15, 2020, in the KoreanIntellectual Property Office, and all the benefits accruing therefromunder 35 U.S.C. § 119, the entire content of which is incorporated byreference herein.

BACKGROUND 1. Field

The present disclosure relates to an epoxy compound, a compositionprepared from the epoxy compound, a semiconductor device prepared fromthe epoxy compound, an electronic device prepared from the epoxycompound, an article prepared from the epoxy compound, and a method ofpreparing the epoxy compound.

2. Description of the Related Art

Due to the trend of manufacturing semiconductor circuits having highcomplexity and high density, thermal stability of molding materials forreleasing heat generated from semiconductor circuits has becomeimportant.

An epoxy molding compound (EMC) including a thermosetting resin is usedas a molding material of a semiconductor package.

An inorganic filler with high thermal conductivity is added to increasethermal conductivity of the EMC.

However, in spite of the addition of the high-thermal-conductivityinorganic filler, the increase in thermal conductivity of the EMC isinsignificant.

SUMMARY

Provided are epoxy compounds having improved heat releasingcharacteristics and processing characteristics which may be easilysynthesized by having a novel structure.

Provided are epoxy resin compositions including the epoxy compounds.

Provided are semiconductor devices including cured products obtainedfrom the compositions.

Provided are electronic devices including cured products obtained fromthe compositions.

Provided are articles including cured products obtained from thecompositions.

Provided are methods of preparing the epoxy compounds.

Additional aspects will be set forth in part in the description whichfollows and, in part, will be apparent from the description, or may belearned by practice of the presented embodiments of the disclosure.

According to an aspect of an embodiment,

-   -   an epoxy compound including an aromatic ring is represented by        Formula 1 or Formula 2:

E1-(M1)_(a1)-(L1)_(b1)-(M2)_(a2)-L2-A1-L3-(M3)_(a3)-(L4)_(b2)-(M4)_(a4)-E2  Formula1

E3-(A2)_(c1)-(L5)_(b3)-(M5)_(a5)-L6-(M6)_(a6)-L7-(M7)_(a7)-(L8)_(b4)-(A3)_(c2)-E4  Formula2

In Formulae 1 and 2,

-   -   M1, M4, M5, and M7 are each independently an arylene group        represented by Formulae 3a to 3j,    -   M2, M3, and M6 are each independently a naphthalene group        represented by Formulae 3g to 3j,

-   -   wherein, in Formulae 3a to 3j,    -   R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, and R₁₂ are each        independently a hydrogen, a halogen, a hydroxy group, or a        substituted or unsubstituted C1-C10 alkyl group;    -   A1, A2, and A3 are each independently a substituted or        unsubstituted C4-C12 alkylene group, a substituted or        unsubstituted C4-C12 alkenylene group, a substituted or        unsubstituted C4-C12 alkynylene group, a substituted or        unsubstituted C4-C12 alkadienylene group, or a (poly)oxyalkylene        group containing a substituted or unsubstituted C1-C5 alkylene        group;    -   L1, L2, L3, L4, L5, L6, L7, and L8 are each independently        —C(═O)O— or —OC(═O)—,    -   E1, E2, E3, and E4 are each independently an epoxy-containing        group,

a1, a4, b1, b2, b3, b4, c1, and c2 are each independently 0 or 1, anda2, a3, a5, a6, and a7 are each independently 1 or 2.

According to an aspect of an embodiment, an epoxy resin compositionincludes;

-   -   the epoxy compound; and    -   a curing agent.

According to an aspect of an embodiment, a semiconductor deviceincludes;

-   -   a substrate; a semiconductor; and    -   a cured product of an epoxy resin composition including a curing        agent, and an epoxy compound represented by Formula 1, an epoxy        compound represented by Formula 2, or a combination thereof,    -   a sealing portion including the cured product of the epoxy resin        composition,    -   a substrate portion including the cured product of the epoxy        resin composition,    -   a reinforcement portion including the cured product of the epoxy        resin composition, or    -   an adhesive portion including the cured product of the epoxy        resin composition.

According to an aspect of an embodiment, an electronic device includes

-   -   a substrate;    -   an electronic component; and    -   a cured product of an epoxy resin composition including a curing        agent, and an epoxy compound represented by Formula 1, an epoxy        compound represented by Formula 2, or a combination thereof,    -   a sealing portion including the cured product of the epoxy resin        composition,    -   a substrate portion including the cured product of the epoxy        resin composition,    -   a reinforcement portion including the cured product of the epoxy        resin composition, or    -   an adhesive portion including the cured product of the epoxy        resin composition.

According to an aspect of an embodiment, an article includes

-   -   a substrate; and    -   a cured product of an epoxy resin composition including a curing        agent, and an epoxy compound represented by Formula 1, an epoxy        compound by Formula 2, or a combination thereof,    -   a sealing portion including the cured product of the epoxy resin        composition,    -   a substrate portion including the cured product of the epoxy        resin composition,    -   a reinforcement portion including the cured product of the epoxy        resin composition, or    -   an adhesive portion including the cured product of the epoxy        resin composition.

According to an aspect of an embodiment, a method of preparing an epoxycompound includes

-   -   providing a first composition by contacting a compound        represented by Formula 11 with a compound represented by Formula        12;    -   preparing a second composition including a compound represented        by Formula 1 from the first composition; and    -   recovering the second composition,

wherein the recovering of the second composition is performed while theproviding of the first composition is being performed.

E1-(M1)_(a1)-(L1)_(b1)-(M2)_(a2)-L2-A1-L3-(M3)_(a3)-(L4)_(b2)-(M4)_(a4)-E2  Formula1

R_(c)-(M1)_(a1)-(L1)_(b1)-(M2)_(a2)-L2-A1-L3-(M3)_(a3)-(L4)_(b2)-(M4)_(a4)-R_(d)  Formula11

E-R_(e)  Formula 12

In Formulae 1, 11, and 12,

-   -   M1, M4, M5, and M7 are each independently an arylene group        represented by Formulae 3a to 3j,    -   M2, M3, and M6 are each independently a naphthalene group        represented by Formulae 3g to 3j,

-   -   wherein, in Formulae 3a to 3j,    -   R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, and R₁₂ are each        independently a hydrogen, a halogen, a hydroxy group, or a        substituted or unsubstituted C1-C10 alkyl group,    -   R_(c), and R_(d) are each independently a hydroxy group, and    -   R_(e) is a halogen;    -   A1, A2, and A3 are each independently a substituted or        unsubstituted C4-C12 alkylene group, a substituted or        unsubstituted C4-C12 alkenylene group, a substituted or        unsubstituted C4-C12 alkynylene group, a substituted or        unsubstituted C4-C12 alkadienylene group, or a (poly)oxyalkylene        group containing a substituted or unsubstituted C1-C5 alkylene        group;    -   L1, L2, L3, L4, L5, L6, L7, and L8 are each independently        —C(═O)O— or —OC(═O)—,    -   E1, E2, and E are each independently an epoxy-containing group,    -   a1, a4, b1, b2, b3, b4, c1, and c2 are each independently 0 or        1, and a2, a3, a5, a6, and a7 are each independently 1 or 2.

BRIEF DESCRIPTION OF THE DRAWINGS

The above and other aspects, features, and advantages of certainembodiments of the disclosure will be more apparent from the followingdescription taken in conjunction with the accompanying drawings, inwhich:

FIG. 1 is a graph that shows changes in thermal conductivity of acompound according to thermal conductivity of a filler;

FIG. 2 is a graph that shows changes in thermal conductivity of acompound according to thermal conductivity of a resin;

FIG. 3 is a schematic cross-sectional view of a semiconductor deviceaccording to an embodiment;

FIG. 4 is a schematic cross-sectional view of an electronic deviceaccording to an embodiment; and

FIG. 5 is a schematic plan view of the electronic device according to anembodiment.

FIG. 6 is a flowchart of an exemplary reaction of Example 1.

DETAILED DESCRIPTION

Reference will now be made in detail to embodiments, examples of whichare illustrated in the accompanying drawings, wherein like referencenumerals refer to like elements throughout. In this regard, the presentembodiments may have different forms and should not be construed asbeing limited to the descriptions set forth herein. Accordingly, theembodiments are merely described below, by referring to the figures, toexplain aspects. As used herein, the term “and/or” includes any and allcombinations of one or more of the associated listed items. Expressionssuch as “at least one of,” when preceding a list of elements, modify theentire list of elements and do not modify the individual elements of thelist, for example, “at least one of a, b, or c” indicates only a, onlyb, only c, both a and b, both a and c, both b and c, all of a, b, and c,or variations thereof.

Various example embodiments will now be described with reference to theaccompanying drawings. This inventive concept may, however, be embodiedin many different forms and should not be construed as limited to theexemplary embodiments set forth herein. Rather, these embodiments areprovided so that this disclosure will be thorough and complete, and willfully convey the scope of the inventive concept to one of ordinary skillin the art. Like reference numerals in the drawings denote likeelements.

It will be understood that when a component is referred to as being “on”another component, the component can be directly on the other componentor intervening components may be present thereon. In contrast, when acomponent is referred to as being “directly on” another component, anintervening component is not present therebetween.

While such terms as “first,” “second,” “third,” etc., may be used todescribe various elements, components, regions, layers, and/or sections,such elements, components, regions, layers, and/or sections must not belimited to the above terms. The above terms are used only to distinguishone element, component, region, layer, or section from another element,component, region, layer, or section. Therefore, a first element,component, region, layer, or section described hereinafter may bereferred to as a second element, component, region, layer, or sectionwithout departing from the teachings of the present specification.

The terms used in the present specification are merely used to describeparticular embodiments, and are not intended to limit the inventiveconcept. An expression used in the singular encompasses the expressionof the plural including “at least one,” unless it has a clearlydifferent meaning in the context. The term “at least one” should not beunderstood as limiting to the singular. As used herein, the term “or”means “and/or,” the term “and/or” includes any and all combinations ofone or more of the associated list items. It will be further understoodthat the terms “includes,” “have,” “comprises,” “including,” “having,”and/or “comprising,” when used in this specification, specify thepresence of stated features, regions, integers, steps, operations,elements, and/or components, but do not preclude the presence oraddition of one or more other features, regions, integers, steps,operations, elements, components, and/or groups thereof.

Spatially relative terms, such as “beneath,” “below,” “lower,” “above,”and “upper,” may be used herein for ease of description to describe oneelement or feature's relationship to another element(s) or feature(s) asillustrated in the figures. It will be understood that the spatiallyrelative terms are intended to encompass different orientations of thedevice in use or operation in addition to the orientation depicted inthe figures. For example, if the device in the figures is turned over,elements described as “below” or “beneath” other elements or featureswould then be oriented “above” the other elements or features. Thus,term such as “below” can encompass both an orientation of above andbelow. The device may be otherwise oriented (rotated 90 degrees or atother orientations), and the spatially relative descriptors used hereinmay be interpreted accordingly.

Unless otherwise defined, all terms (including technical and scientificterms) used herein have the same meaning as commonly understood by oneof ordinary skill in the art to which this invention belongs. It will befurther understood that terms, such as those defined in commonly useddictionaries, should be interpreted as having a meaning that isconsistent with their meaning in the context of the relevant art andwill not be interpreted in an idealized or overly formal sense unlessexpressly so defined herein.

Example embodiments are described herein with reference tocross-sectional illustrations that are schematic illustrations ofidealized example embodiments. As such, variations from the shapes ofthe illustrations as a result, for example, of manufacturing techniquesand/or tolerances, are to be expected. Thus, example embodiments shouldnot be construed as limited to the particular shapes of regionsillustrated herein but are to include deviations in shapes that result,for example, from manufacturing. For example, a region illustrated ordescribed as flat may, typically, have rough and/or nonlinear features.Moreover, angles illustrated as sharp may be rounded. Thus, the regionsillustrated in the figures are schematic in nature and their shapes arenot intended to illustrate the actual shape of a region and are notintended to limit the scope of the present description.

“About” or “approximately” as used herein is inclusive of the statedvalue and means within an acceptable range of deviation for theparticular value as determined by one of ordinary skill in the art,considering the measurement in question and the error associated withmeasurement of the particular quantity (i.e., the limitations of themeasurement system). For example, “about” can mean within one or morestandard deviations, or within ±20%, 10%, 5% of the stated value.

While particular embodiments are described, alternatives, modifications,variations, improvements, and substantial equivalents that are or may bepresently unforeseen or unexpected may arise to applicants or thoseskilled in the art. Accordingly, the appended claims as filed and asthey may be amended are intended to embrace all such alternatives,modification, variations, improvements, and substantial equivalents.

Hereinafter, according to an embodiment, an epoxy compound, acomposition prepared from the epoxy compound, a semiconductor deviceprepared from the epoxy compound, an electronic device prepared from theepoxy compound, an article prepared from the epoxy compound, and amethod of preparing the article will be described in detail. Composition(I)

An epoxy compound according to an embodiment is an epoxy compoundincluding an aromatic ring represented by Formula 1 or Formula 2:

E1-(M1)_(a1)-(L1)_(b1)-(M2)_(a2)-L2-A1-L3-(M3)_(a3)-(L4)_(b2)-(M4)_(a4)-E2  Formula1

E3-(A2)_(c1)-(L5)_(b3)-(M5)_(a5)-L6-(M6)_(a6)-L7-(M7)_(a7)-(L8)_(b4)-(A3)_(c2)-E4  Formula2

In Formulae 1 and 2,

-   -   M1, M4, M5, and M7 are each independently an arylene group        represented by Formula 3a to 3j,    -   M2, M3, and M6 are each independently a naphthalene group        represented by Formula 3g to 3j,

-   -   wherein, in Formulae 3a to 3j,    -   R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, and R₁₂ are each        independently a hydrogen, a halogen, a hydroxy group, or a        substituted or unsubstituted C1-C10 alkyl group;    -   A1, A2, and A3 are each independently a substituted or        unsubstituted C4-C12 alkylene group, a substituted or        unsubstituted C4-C12 alkenylene group, a substituted or        unsubstituted C4-C12 alkynylene group, a substituted or        unsubstituted C4-C12 alkadienylene group, or a (poly)oxyalkylene        group containing a substituted or unsubstituted C1-C5 alkylene        group;    -   L1, L2, L3, L4, L5, L6, L7, and L8 are each independently        —C(═O)—, —S(═O)—, —C(═O)O—, —OC(═O)—, —S(═O)O—, —OS(═O)—,        —O—C(═O)O—, —(CH₂)₂—C(═O)—, —C(═O)—(CH₂)₂—, —C(═O)—CH═CH—,        —CH═CH—C(═O)—, —CH═N—, —N═CH—, —NH—C(═O)O—, —C(═O)—NH—, or        —OC(═O)—NH—S(═O)O—,    -   E1, E2, E3, and E4 are each independently an epoxy-containing        group,    -   a1, a4, b1, b2, b3, b4, c1, and c2 are each independently 0 or        1, and a2, a3, a5, a6, and a7 are each independently 1 or 2.

In Formula 1 and Formula 2, for example, L1, L2, L3, L4, L5, L6, L7, andL8 are each independently —C(═O)O— or —OC(═O)—.

In Formula 1 and Formula 2, A1, A2, and A3 may be each independently,for example, a C4-C12 alkylene group unsubstituted or substituted with ahalogen, a C4-C12 alkenylene group unsubstituted or substituted with ahalogen, a C4-C12 alkynylene group unsubstituted or substituted with ahalogen, a C4-C12 alkadienylene group unsubstituted or substituted witha halogen, or a (poly)oxyalkylene group containing a C1-C5 alkylenegroup unsubstituted or substituted with a halogen. The halogen may be,for example, F, Cl, Br, or I. The halogen may be, for example, F.

The resin is generally a thermal insulator, and a thermal conductivityof the resin is about 0.2 Watts per meter Kelvin (W/mK) or less. Heat istransferred in a resin, which is a thermal insulator, by vibrationtransmission of phonons, but a thermal conductivity of the resin maybecome low because of a scattering of phonons. A thermal conductivity ofa resin that is used as a semiconductor package material may be, forexample, in a range of about 0.1 W/mK to about 0.2 W/mK. Even when afiller having a high thermal conductivity is added to the resin, anincrease in thermal conductivity of the compound (e.g., epoxy moldingcompound) is not significant. For example, FIG. 1 is a graph that showschanges in thermal conductivity of a compound (e.g., epoxy moldingcompound) according to thermal conductivity of a filler. FIG. 1 showsthat a thermal conductivity of a compound including a filler and a resin(e.g., epoxy molding compound) as an amount of the filler increased fromabout 1 vol % to about 90 vol % in the resin having a thermalconductivity of about 0.2 W/mK, where the results are calculated basedon the Maxwell Model. As shown in FIG. 1, at an amount of the filler ofabout 90 vol %, a thermal conductivity of the compound (e.g., epoxymolding compound) converges to about 5 W/mK even when a thermalconductivity of the filler increases to about 50 W/mK or more. That is,in the compound including the filler and the resin (e.g., epoxy moldingcompound), a thermal conductivity of the compound converges to about 5W/mK and does not increase any higher even when a thermal conductivityof the filler increases to about 100 W/mK.

In an embodiment, the epoxy compound including an aromatic ringrepresented by Formula 1 or Formula 2 has a mesogenic unit that containsa plurality of aromatic rings in the main chain. While not wishing to bebound by theory, it is understood that as the plurality of aromaticrings in the mesogenic unit form π-π stacking and intermolecularhydrogen bonding, chain stiffness of the main chain of the epoxycompound may increase, and molecular ordering of the epoxy compound mayincrease. As a result, a phonon transfer pathway may be provided in theresin, which is an epoxy compound and/or its cured product. Thus,thermal conductivity of the epoxy compound and/or its cured product mayincrease. In an embodiment, the epoxy compound including an aromaticring represented by Formula 1 or Formula 2 may further include a spacerhaving flexibility between the mesogenic units or on one surface of themesogenic unit. As the spacer is further introduced in the epoxycompound, for example, a liquid crystal like structure such as a smecticphase may be formed. Molecular ordering of an epoxy compound and/or anda resin prepared therefrom may increase by including a high ordereddomain such as the liquid crystal like structure. As a result, phononscattering in the resin, which is an epoxy compound and/or its curedproduct, may be suppressed. In an embodiment, the epoxy compoundincluding an aromatic ring represented by Formula 1 or Formula 2 has amesogenic unit and a spacer linked by an ester bond. As the mesogenicunit and the spacer are linked by an ester bond, liquid crystallinity ofthe epoxy compound including an aromatic ring represented by Formula 1or Formula 2 may further be improved. In an embodiment, thermalconductivity of the resin, which is an epoxy compound and/or its curedproduct may further be increased. Therefore, when thermal conductivityof the resin, which is a cured product obtained from the epoxy compoundrepresented by Formula 1 and/or Formula 2, is high, the thermalconductivity of the compound including the resin (e.g., epoxy moldingcompound) was significantly increased. For example, FIG. 2 is a graphthat shows changes in thermal conductivity of the compound (e.g., epoxymolding compound) according to thermal conductivity of the resin. FIG. 2shows the results changes in a thermal conductivity value of a compoundincluding a filler and a resin according to an amount of the fillerwhile a thermal conductivity of an Al₂O₃ filler is fixed to a thermalconductivity of about 50 W/mK and a thermal conductivity of the resin isincreased from about 0.2 W/mK to about 1.0 W/mK, where the results arecalculated based on the Maxwell Model. As shown in FIG. 2, at an amountof the filler of about 90 vol %, a thermal conductivity of the compound(e.g., epoxy molding compound) increased up to about 18 W/mK, when athermal conductivity of the resin is increased from about 0.2 W/mK toabout 1.0 W/mK.

The epoxy compound including an aromatic ring represented by Formula 1may be, for example, an epoxy compound represented by one of Formulae 4ato 4f

E1-M2-L2-A1-L3-M3-E2  Formula 4a

E1-M1-L1-M2-L2-A1-L3-M3-E2  Formula 4b

E1-M2-L2-A1-L3-M3-L4-M4-E2  Formula 4c

E1-M1-L1-M2-L2-A1-L3-M3-L4-M4-E2  Formula 4d

E1-M1-M2-L2-A1-L3-M3-L4-M4-E2  Formula 4e

E1-M1-L1-M2-L2-A1-L3-M3-M4-E2  Formula 4f

In Formulae 4a to 4f,

-   -   M1 and M4 are each independently an arylene group represented by        Formulae 3a to 3j,    -   M2 and M3 are each independently a naphthalene group represented        by Formulae 4a to 4d,    -   A1 is a substituted or unsubstituted C4-C12 alkylene group, a        substituted or unsubstituted C4-C12 alkenylene group, a        substituted or unsubstituted C4-C12 alkynylene group, a        substituted or unsubstituted C4-C12 alkadienylene group, or a        (poly)oxyalkylene group containing a substituted or        unsubstituted C1-C5 alkylene group;    -   L1, L2, L3, and L4 are each independently —C(═O)O— or —OC(═O)—,    -   E1, E2, E3, and E4 are each independently an epoxy-containing        group.

The epoxy compound including an aromatic ring represented by Formula 2may be, for example, an epoxy compound represented by one of Formulae 5ato 5f:

E3-A2-L5-M5-L6-M6-L7-M7-L8-A3-E4  Formula 5a

E3-M5-L6-M6-L7-M7-L8-A3-E4  Formula 5b

E3-A2-L5-M5-L6-M6-L7-M7-E4  Formula 5c

E3-A2-L6-M6-L7-M7-L8-A3-E4  Formula 5d

E3-A2-L5-M5-L6-M6-L7-A3-E4  Formula 5e

In Formulae 5a to 5f,

-   -   M5 and M7 are each independently an arylene group represented by        Formulae 3a to 3j,    -   M6 is a naphthalene group represented by Formulae 4a to 4d,    -   A2 and A3 are each independently a substituted or unsubstituted        C4-C12 alkylene group, a substituted or unsubstituted C4-C12        alkenylene group, a substituted or unsubstituted C4-C12        alkynylene group, a substituted or unsubstituted C4-C12        alkadienylene group, or a (poly)oxyalkylene group containing a        substituted or unsubstituted C1-C5 alkylene group;    -   L5, L6, L7, and L8 are each independently —C(═O)O— or —OC(═O)—,    -   E1, E2, E3, and E4 are each independently an epoxy-containing        group.

In the epoxy compound represented by one of Formulae 1 to 5e, A1, A2,and A3 may be each independently, for example, an ethylene group, apropylene group, a butylene group, a pentylene group, a hexylene group,a heptylene group, an octylene group, a nonylene group, a decylenegroup, an undecylene group, a dodecylene group, a butadienylene group, apentadienylene group, a hexadienylene group, a heptadienylene group, anoctadienylene group, a nonadienylene group, a decadienylene group, anundecadienylene group, a dodecadienylene group, or —(CH₂O)p- (where p isa real number of 1 to 10).

In the epoxy compound represented by one of Formulae 1 to 5e, L1, L2,L3, L4, L5, L6, L7, and L8 may be each independently, for example,—C(═O)O— or —OC(═O)—.

In the epoxy compound represented by one of Formulae 1 to 5e, E1 and E2may be each independently, for example, epoxy-containing groupsrepresented by Formulae 6a to 6d:

In Formulae 6a to 6f,

-   -   R_(a), and R_(b) are each independently a hydrogen, a halogen, a        hydroxy group, or a substituted or unsubstituted C1-C10 alkyl        group,    -   n1 is 2 to 10, and n2 is 1 to 10.

In the epoxy compound represented by one of Formulae 1 to 5e, M1, M4,M5, and M7 may be each independently an arylene group represented byFormulae 7a to 7j, M2, M3, and M6 may be each independently anaphthalene group represented by Formulae 7g to 7j, and E1 and E may beeach independently epoxy-containing groups represented by Formulae 8a to8f:

In Formulae 7a to 7j and 8 a to 8f, n1 is 1 to 10, and n2 is 2 to 10.

The epoxy compound represented by Formula 1 may be, for example, anepoxy compound represented by one of Formulae 9a to 9p:

The epoxy compound represented by Formula 2 may be, for example, anepoxy compound represented by one of Formulae 10a to 10p:

By including a spacer A1, A2, or A3, the epoxy compound represented byFormula 1 or Formula 2 may have a melting temperature lower than that ofany conventional or any suitable epoxy compound. The melting temperatureof the epoxy compound represented by Formula 1 or Formula 2 may be, forexample, about 200° C. or lower, about 195° C. or lower, about 190° C.or lower, about 185° C. or lower, about 180° C. or lower, about 175° C.or lower, about 170° C. or lower, about 165° C. or lower, about 160° C.or lower, about 155° C. or lower, about 150° C. or lower, about 145° C.or lower, about 140° C. or lower, about 135° C. or lower, or about 130°C. or lower. The melting temperature of the epoxy compound representedby Formula 1 or Formula 2 may be, for example, in a range of about 30°C. to about 200° C., about 50° C. to about 195° C., about 70° C. toabout 190° C., about 90° C. to about 185° C., about 100° C. to about180° C., about 100° C. to about 175° C., about 100° C. to about 170° C.,about 100° C. to about 165° C., about 100° C. to about 160° C., about100° C. to about 155° C., about 100° C. to about 150° C., about 100° C.to about 145° C., about 100° C. to about 140° C., about 100° C. to about135° C., or about 100° C. to about 130° C. When the epoxy compoundrepresented by Formula 1 or Formula 2 has a melting point within theseranges, a curing temperature of the epoxy resin composition obtainedfrom the epoxy compound represented by Formula 1 or Formula 2 may belowered. As the epoxy resin composition has such a low curingtemperature, damages such as thermal deformation of electroniccomponents that may occur during a curing process at a high-temperaturemay be prevented.

Epoxy Resin Composition

An epoxy resin composition according to an embodiment includes an epoxycompound represented by one of Formula 1, Formula 2, Formulae 4a to 4f,Formulae 5a to 5e, Formulae 9a to 9p, and Formulae 10a to 10p; and acuring agent. When the epoxy resin composition includes the epoxycompound, a cured product of the epoxy resin composition may provideimproved thermal conductivity. The epoxy resin composition may be moldedinto various forms.

The curing agent in the epoxy resin composition may be, for example, anamine-based curing agent, an acid anhydride-based curing agent, apolyamine curing agent, a polysulfide curing agent, a phenol novolaktype curing agent, a bisphenol A type curing agent, or a dicyandiamidecuring agent, but embodiments are not limited thereto. The curing agentmay be, for example, a polyfunctional phenol-based curing agent. Thepolyfunctional phenol-based curing agent may be, for example, a compoundhaving at least three phenolic hydroxyl groups, and the compound mayhave the following structure.

-   -   wherein n in the formula above is an integer of 1 to 10000.

A number average molecular weight of the polyfunctional phenol-basedcuring agent may be, for example, in a range of about 300 daltons toabout 30000 daltons, about 400 daltons to about 30000 daltons, about 600daltons to about 10000 daltons, or about 800 daltons to about 10000daltons.

An amount of the curing agent may be in a range of about 0.1 parts toabout 10 parts by weight, about 0.1 parts to about 5 parts, or about 0.1parts to about 1 part by weight based on 100 parts by weight of theepoxy resin composition, but embodiments are not limited thereto. Whenan amount of the curing agent is within these ranges, deterioration ofinsulating characteristics of the compound may be prevented byminimizing an amount of an unreacted curing agent while increasing acuring rate of the epoxy resin composition.

The epoxy resin composition may not include metal ions. The epoxy resincomposition may substantially not include metal ions. An amount of themetal ions in the epoxy resin composition may be about 10 parts permillion (ppm) or less, about 5 ppm or less, about 3 ppm or less, about 2ppm or less, or about 1 ppm or less. For example, the amount of themetal ions in the epoxy resin composition may be about 0.1 ppm to about10 ppm, about 0.5 ppm to about 10 ppm, about 1 ppm to about 10 ppm,about 2 ppm to about 10 ppm, about 3 ppm to about 10 ppm, about 4 ppm toabout 10 ppm, about 5 ppm to about 10 ppm, about 6 ppm to about 10 ppm,about 7 ppm to about 10 ppm, about 8 ppm to about 10 ppm, or about 9 ppmto about 10 ppm.

The epoxy compound represented by Formula 1 or 2 used in the epoxy resincomposition may not include metal ions as impurities. The epoxy compoundrepresented by Formula 1 or 2 used in the epoxy resin composition maynot include metal ions as impurities. An amount of the metal ions asimpurities in the epoxy resin composition may be about 3 ppm or less,about 2 ppm or less, about 1 ppm or less, about 0.5 ppm or less, orabout 0.1 ppm or less. For example, the amount of the metal ions asimpurities in the epoxy resin composition may be about 0.1 ppm to about3 ppm, about 0.5 ppm to about 3 ppm, about 1 ppm to about 3 ppm, orabout 2 ppm to about 3 ppm.

The epoxy resin composition may further include, for example, a filler,and the filler may be an inorganic filler, an organic filler, or acombination thereof.

The inorganic filler may be, for example, at least one of silicon oxide,calcium carbonate, magnesium carbonate, alumina, magnesia, clay, alumina(Al₂O₃), titania (TiO₂), talc, calcium silicate, antimony oxide, glassfiber, or eucryptite ceramic, but embodiments are not limited thereto.The eucryptite ceramic may be a crystallized glass formed of Li₂O,Al₂O₃, and SiO₂ components. The organic filler may include, for example,at least one of polyethylene imine, ethylene glycol, or polyethyleneglycol, but embodiments are not limited thereto. The filler may be aninorganic filler in terms of having high thermal conductivity,strengthening the rigidity of the compound, and reducing the linearexpansion coefficient.

An amount of the filler may be, for example, in a range of about 20weight % (wt %) to about 99 wt %, about 30 wt % to about 99 wt %, about40 wt % to about 99 wt %, about 50 wt % to about 99 wt %, about 60 wt %to about 99 wt %, about 70 wt % to about 99 wt %, about 80 wt % to about99 wt %, about 90 wt % to about 99 wt %, or about 95 wt % to about 99 wt% based on the total weight of the epoxy resin composition. When anamount of the filler in the epoxy resin composition is within theseranges, properties such as moldability, low-stress property,high-temperature strength, and thermal expansion coefficient may beeffectively controlled.

The epoxy resin composition may further include at least one additivefrom a curing accelerator, a reaction modifier, a releasing agent, acoupling agent, a stress reliever, or an auxiliary flame retardant. Theadditives may be each independently included in the epoxy resincomposition at an amount, for example, in a range of about 0.1 parts toabout 10 parts by weight, about 0.1 parts to about 5 parts by weight,about 0.1 parts to about 3 parts by weight, or about 0.1 parts to about1 part by weight based on 100 parts by weight of the epoxy resincomposition.

The epoxy resin composition may further include any conventional or anysuitable epoxy resins in addition to the epoxy compound according to anembodiment. When the epoxy resin composition includes any conventionalor any suitable epoxy resins, thermal expansion coefficient, warpage,and processing characteristics of the compound may further be improved,and peeling strength of the epoxy resin composition may also beimproved. Examples of the conventional or suitable epoxy resins mayinclude a biphenyl epoxy resin, a novolac epoxy resin, adicyclopentadienyl epoxy resin, a bisphenol epoxy resin, a terpene epoxyresin, an aralkyl epoxy resin, a multi-functional epoxy resin, anaphthalene epoxy resin, and a halogenated epoxy resin. These epoxyresins may be used alone or in a mixture of two or more. An amount ofthe conventional or suitable epoxy resin may be, for example, in a rangeof about 1 part to about 15 parts by weight, about 1 part to about 10parts by weight, about 1 part to about 5 parts by weight based on 100parts by weight of the epoxy resin composition, but embodiments are notlimited thereto. When the epoxy resin composition further includes theconventional or suitable epoxy resin at an amount within these ranges,for example, adhesion between the epoxy resin composition and asubstrate on a semiconductor package, thermal expansion coefficient, andprocessing properties of the compound may further be improved.

The epoxy resin composition may be used for various purposes. Forexample, the epoxy resin composition may be used as an encapsulatingresin composition or a fixing resin composition. The encapsulating resincomposition (a resin composition for encapsulating an electroniccompartment) may be, for example, a resin composition for encapsulatinga semiconductor capable of encapsulating electronic compartments such asa semiconductor chip and used in a semiconductor package, a resincomposition for encapsulating electronic control units for vehicles, inwhich a substrate having electronic compartments mounted thereon isencapsulated, or a resin composition for encapsulating a sensor, asensor module, a camera, a camera module, a module with an indicator, amodule with a battery, or a module with a coin battery. The fixing resincomposition may be, for example, a fixing resin composition of a motorcompartment. The fixing resin composition of a motor compartment may be,for example, a resin composition for fixing a rotor core magnet or forfixing a stator. The epoxy resin composition may be used for purposesother than those described above.

A method of preparing an epoxy resin composition is not particularlylimited. The method of preparing an epoxy resin composition may includeselecting ingredients such as an epoxy compound and a curing agent; andmixing the ingredients. For example, an epoxy compound appropriate foran epoxy resin composition may be represented by Formula 1 and/orFormula 2. Subsequently, the epoxy compound may be mixed with otheringredients such as a curing agent or an additive to prepare a mixtureas an epoxy resin composition.

In the mixing of the ingredients, the mixture may be obtained using anysuitable method. Also, the mixture may be, for example, melt-kneaded ata temperature lower than the curing temperature of the epoxy resincomposition to obtain a kneaded product. As the kneading method, forexample, a kneading extruder such as a monoaxial kneading extruder or abiaxial kneading extruder may be used or a roll-type kneader such as amixing roll may be used, but the biaxial kneading extruder may be used.After cooling the kneaded product in the melted state, the kneadedproduct may be molded into a powdery, granular, tablet, or sheet shape.As a method of preparing a resin composition of a powdery shape, forexample, a method of pulverizing a kneaded product using a pulverizingdevice may be used. The kneaded product may be molded on sheet and thenpulverized. A device used in the pulverization may be, for example, ahammer mill, a mortar grinder, or a roll crusher. A method of preparinga resin composition having a granular shape or a powdery shape mayinclude, for example, an assembly method represented by a hot-cuttechnique, in which a dice having a small diameter is installed on adischarge port of a kneading device, and the molten kneaded productdischarged from the dice is cut into a predetermined length by a cutter.After preparing the resin composition having a granular shape or apowdery shape using the assembly method such as the hot-cut technique,degassing of the resin composition may be performed while thetemperature of the resin composition is not much lowered.

Semiconductor Device

According to an embodiment, a semiconductor device includes a substrate;a semiconductor; and a cured product of an epoxy resin compositionincluding a curing agent and an epoxy compound represented by Formula 1,an epoxy compound represented by Formula 2, or a combination thereof, asealing portion including the cured product of the epoxy resincomposition, a substrate portion including the cured product of theepoxy resin composition, a reinforcement portion including the curedproduct of the epoxy resin composition, or an adhesive portion includingthe cured product of the epoxy resin composition. When the semiconductordevice includes at least one of the cured product, sealing portion,substrate portion, reinforcement portion, or adhesive portion, heatrelease characteristics of the semiconductor device may be improved, andas a result, thermal stability of the semiconductor device may beimproved.

A thermal conductivity of the cured products of the epoxy resincompositions in the semiconductor device may be, for example, about 0.3W/mK or more, about 0.35 W/mK or more, about 0.4 W/mK or more, about0.45 W/mK or more, about 0.5 W/mK or more, about 0.55 W/mK or more, orabout 0.6 W/mK or more. A thermal conductivity of the cured product ofthe epoxy resin composition in the semiconductor device may be, forexample, in a range of about 0.3 W/mK to about 50 W/m K, about 0.3 W/mKto about 45 W/m K, about 0.3 W/mK to about 40 W/m K, about 0.3 W/mK toabout 35 W/m K, about 0.3 W/mK to about 30 W/m K, about 0.3 W/mK toabout 25 W/m K, about 0.3 W/mK to about 20 W/m K, or about 0.3 W/mK toabout 15 W/mK. A thermal conductivity of the cured product of the epoxyresin composition in the semiconductor device may be, for example, in arange of about 0.35 W/mK to about 40 W/mK, about 0.4 W/mK to about 35W/mK, about 0.45 W/mK to about 30 W/m K, about 0.50 W/mK to about 20 W/mK, about 0.55 W/mK to about 15 W/m K, or about 0.6 W/mK to about 10W/mK. When a thermal conductivity of at least one of the cured product,sealing portion, substrate portion, reinforcement portion, or adhesiveportion in the semiconductor device is within these ranges, thermalstability of the semiconductor device may further be improved.

The semiconductor device may be, for example, a semiconductor package.Referring to FIG. 3, a semiconductor package 100 includes a substrate 5;a die attach film 4 placed on the substrate 5; a semiconductor chip 3placed on the substrate 5 and attached to the substrate 5 through thedie attach film 4; coupling portions 6 such as bonding wires thatelectrically connect the semiconductor chip 3 and the substrate 5; and amolding portion 110 that encapsulates the semiconductor chip 3 and thecoupling portions 6 and for protecting the substrate 5 and anaccommodation structure including the semiconductor chip 3 and thecoupling portions 6 mounted on the substrate 5. The molding portion 110is formed to completely encapsulate the semiconductor chip 3 and thecoupling portions 6 on the substrate 5. The molding portion 110 may beprepared from the epoxy resin composition described herein. The moldingportion 110 may include an epoxy resin 1 and fillers 2 dispersed in theepoxy resin 1. The molding portion 110 may have a form in which fillersdispersed in a resin matrix formed by curing an epoxy compound. Aplurality of solder balls 7 that electrically connect the semiconductorchip 3 to an external circuit (not shown) are formed on a surface 5B inthe substrate 5 opposite to an accommodation surface 5A on which thesemiconductor chip 3 is mounted. In order to prepare a semiconductorpackage using an epoxy resin composition, for example, the semiconductorpackage 100 shown in FIG. 3, a process of forming the molding portion110 that encapsulate the semiconductor chip 3 mounted on the substrate 5may be performed using a low-pressure transfer molding process. In anembodiment, for example, an injection molding process or a castingprocess may be used instead of the low-pressure transfer moldingprocess. The molding portion 110 formed using the epoxy resincomposition may protect a region of the semiconductor chip 3 frommoisture in the semiconductor package 100 and provide improved heatrelease characteristics. In an embodiment, the reliability of thesemiconductor package 100 may be improved even in a humid environment.

Electronic Device

According to an embodiment, an electronic device includes a substrate;an electronic component; and a cured product of an epoxy resincomposition including a curing agent, and an epoxy compound representedby Formula 1, an epoxy compound represented by Formula 2, or acombination thereof, a sealing portion including the cured product ofthe epoxy resin composition, a substrate portion including the curedproduct of the epoxy resin composition, a reinforcement portionincluding the cured product of the epoxy resin composition, or anadhesive portion including the cured product of the epoxy resincomposition. When the electronic device includes at least one of thecured product, sealing portion, substrate portion, reinforcementportion, or adhesive portion, heat release characteristics of theelectronic device may be improved, and as a result, thermal stability ofthe electronic device may be improved.

A thermal conductivity of the cured products of the epoxy resincompositions in the electronic device may be, for example, about 0.3W/mK or more, about 0.35 W/mK or more, about 0.4 W/mK or more, about0.45 W/mK or more, about 0.5 W/mK or more, about 0.55 W/mK or more, orabout 0.6 W/mK or more. A thermal conductivity of the cured products ofthe epoxy resin compositions in the electronic device may be, forexample, in a range of about 0.3 W/mK to about 50 W/mK, about 0.3 W/mKto about 45 W/mK, about 0.3 W/mK to about 40 W/mK, about 0.3 W/mK toabout 35 W/mK, about 0.3 W/mK to about 30 W/mK, about 0.3 W/mK to about25 W/mK, about 0.3 W/mK to about 20 W/mK, or about 0.3 W/mK to about 15W/mK. A thermal conductivity of the cured products of the epoxy resincompositions in the electronic device may be, for example, in a range ofabout 0.35 W/mK to about 40 W/mK, about 0.4 W/mK to about 35 W/mK, about0.45 W/mK to about 30 W/mK, about 0.50 W/mK to about 20 W/mK, about 0.55W/mK to about 15 W/mK, or about 0.6 W/mK to about 10 W/mK. When athermal conductivity of at least one of the cured product, sealingportion, substrate portion, reinforcement portion, or adhesive portionin the electronic device is within these ranges, thermal stability ofthe electronic device may further be improved.

The electronic device may be, for example, an electronic control unit, asensor, a sensor module, a camera, a camera module, a module with anindicator, a module with a coin battery, or a motor in which a substratehaving electronic compartments mounted thereon is encapsulated. Theelectronic device may be, for example, an integrated circuit devicehaving electronic components mounted thereon or a printed circuit boardhaving electronic components mounted thereon. Referring to FIG. 4, anintegrated circuit device 300 includes a plurality of semiconductorchips 320 sequentially stacked on a package substrate 310. A controlchip 330 is connected on the plurality of semiconductor chips 320. Astack of the plurality of semiconductor chips 320 and the control chip330 is sealed on the package substrate 310 by a molding portion 340. Themolding portion 340 may have similar features with those of the moldingportion 110 in FIG. 3. The molding portion 340 may be prepared using theepoxy resin composition described herein. The molding portion 340includes an epoxy resin 341 and a plurality of fillers 342 dispersed inthe epoxy resin 341. Details about the epoxy resin 341 and the fillers342 may be the same with those of the epoxy resin 1 and the fillers 2 inFIG. 3. FIG. 4 shows an example structure in which the plurality ofsemiconductor chips 320 are vertically stacked. The plurality ofsemiconductor chips 320 may be arranged in a horizontal direction on thepackage substrate 310 or may be arranged in a combined structure of avertical direction mounting and a horizontal direction mounting. Thecontrol chip 330 may be omitted. The package substrate 310 may be aflexible printed circuit board, a rigid printed circuit board, or acombination thereof. The package substrate 310 includes substrateinternal distribution lines 312 and coupling terminals 314. The couplingterminals 314 may be formed on a surface of the package substrate 310.Solder balls 316 are formed on the other surface of the packagesubstrate 310. The coupling terminals 314 are electrically connected tothe solder balls 316 via the substrate internal distribution lines 312.The solder balls 316 may be replaced by conductive bumps or lead gridarray (LGA). The plurality of semiconductor chips 310 and the controlchip 330 may respectively include coupling structures 322 and 332. Thecoupling structures 322 and 332 may each be formed of, for example, athrough silicon via (TSV) contact structure. The coupling structures 322and 332 in the plurality of semiconductor chips 320 and the control chip330 are electrically connected to the coupling terminals 314 of thepackage substrate 310 via coupling portions 350 such as bumps. Theplurality of semiconductor chips 320 may each include system LSI, flashmemory, DRAM, SRAM, EEPROM, PRAM, MRAM, or RRAM. The control chip 330may include logic circuits such as a serializer/deserializer (SER/DES)circuit. Referring to FIG. 5, an integrated circuit device 400 includesa module substrate 410; and a control chip 420 and a plurality ofsemiconductor packages 430 mounted on the module substrate 410. Aplurality of input/output terminals 450 are formed on the modulesubstrate 410. The plurality of semiconductor package 430 includes atleast one of the semiconductor package 100 of FIG. 3 or the integratedcircuit device 300 of FIG. 4.

Article

According to an embodiment, an article includes a substrate; and a curedproduct of an epoxy resin composition including a curing agent, and anepoxy compound represented by Formula 1, an epoxy compound representedby Formula 2, or a combination thereof, a sealing portion including thecured product of the epoxy resin composition, a substrate portionincluding the cured product of the epoxy resin composition, areinforcement portion including the cured product of the epoxy resincomposition, or an adhesive portion including the cured product of theepoxy resin composition. When the article includes at least one of thecured product, sealing portion, substrate portion, reinforcementportion, or adhesive portion, heat release characteristics of thearticle may be improved, and as a result, thermal stability of thearticle may be improved.

A thermal conductivity of the cured products of the epoxy resincompositions in the article may be, for example, about 0.3 W/mK or more,about 0.35 W/mK or more, about 0.4 W/mK or more, about 0.45 W/mK ormore, about 0.5 W/mK or more, about 0.55 W/mK or more, or about 0.6 W/mKor more. A thermal conductivity of the cured products of the epoxy resincompositions in the article may be, for example, in a range of about 0.3W/mK to about 50 W/mK, about 0.3 W/mK to about 45 W/mK, about 0.3 W/mKto about 40 W/mK, about 0.3 W/mK to about 35 W/m K, about 0.3 W/mK toabout 25 W/m K, about 0.3 W/mK to about 20 W/m K, or about 0.3 W/mK toabout 15 W/mK. A thermal conductivity of the cured products of the epoxyresin compositions in the article may be, for example, in a range ofabout 0.35 W/mK to about 40 W/mK, about 0.4 W/mK to about 35 W/mK, about0.45 W/mK to about 30 W/m K, about 0.50 W/mK to about 20 W/m K, about0.55 W/mK to about 15 W/m K, or about 0.6 W/mK to about 10 W/mK. When athermal conductivity of at least one of the cured product, sealingportion, substrate portion, reinforcement portion, or adhesive portionin the article is within these ranges, thermal stability of the articlemay further be improved.

The article may be, for example, an MP3 player, a navigation system, aportable multimedia player (PMP), a solid state disk (SSD), or ahousehold appliance, but embodiments are not limited thereto.

According to an embodiment, a method of preparing an article includesproviding the epoxy resin composition described herein on a substrate;and curing the epoxy resin composition.

The epoxy resin composition may be provided in various state such as aliquid state, a solid state, and a semi-cured state on the substrate.The epoxy resin composition provided in a liquid state may be providedin a molten state or a state dissolved in a solvent. The epoxy resincomposition provided in a liquid state may be provided in various shapessuch as a powdery shape, a granular shape, or a sheet shape on thesubstrate. The epoxy resin composition may be provided in a state notcured at all, partially cured, or in a semi-cured state on thesubstrate. The epoxy resin composition may be molded into apredetermined shape after being provided on the substrate or may beprovided on the substrate after being molded into a predetermined shape.

Once the epoxy resin composition is provided on the substrate, the epoxyresin composition may be cured to prepare an article. The cured epoxyresin composition may form a sealing portion, a substrate portion, areinforcement portion, or an adhesive portion of the article, butembodiments are not limited thereto.

A method of curing the epoxy resin composition may include thermalcuring or ultraviolet light curing, but embodiments are not limitedthereto. The epoxy resin composition may be cured by heat. A curingtemperature of the epoxy resin composition may be about 100° C. orhigher, about 110° C. or higher, or about 120° C. or higher. A curingtemperature of the epoxy resin composition may be, for example, about200° C. or lower, about 195° C. or lower, about 190° C. or lower, about185° C. or lower, or about 180° C. or lower. A curing temperature of theepoxy resin composition may be, for example, in a range of about 100° C.to about 200° C., about 110° C. to about 200° C., about 120° C. to about200° C., about 130° C. to about 200° C., about 150° C. to about 195° C.,about 160° C. to about 190° C., about 150° C. to about 185° C., or about150° C. to about 180° C. When the epoxy resin composition is cured at acuring temperature within these ranges, damages caused by thermaldeformation of a semiconductor or electronic components may beprevented.

Method of Preparing Epoxy Compound

In order to improve thermal conductivity of an epoxy molding compound(EMC), improvement of an epoxy resin itself is important, and the helpof a liquid crystal mesogenic unit is useful. However, introduction of aliquid crystal mesogenic unit into an epoxy resin structure may increasea melting point of an epoxy resin and thus may deteriorateprocessability of an epoxy compound. An alkyl group, which is flexible,may be introduced to lower the melting point of the epoxy resin.However, an epoxy resin compound, to which an alkyl group is introduced,is difficult to be synthesized, and it takes a long period of time forthe synthesis. Therefore, a method of preparing an epoxy compound in asimple process and in a short period of time is needed.

According to an embodiment, a method of preparing an epoxy compoundincludes providing a first composition by contacting a compoundrepresented by Formula 11 with a compound represented by Formula 12;preparing a second composition including a compound represented byFormula 1 from the first composition; and recovering the secondcomposition, wherein the recovering of the second composition isperformed while the providing of the first composition is beingperformed:

E1-(M1)_(a1)-(L1)_(b1)-(M2)_(a2)-L2-A1-L3-(M3)_(a3)-(L4)_(b2)-(M4)_(a4)-E2  Formula1

R_(c)-(M1)_(a1)-(L1)_(b1)-(M2)_(a2)-L2-A1-L3-(M3)_(a3)-(L4)_(b2)-(M4)_(a4)-R_(d)  Formula11

E-R_(e)  Formula 12

-   -   wherein in Formulae 1, 11, and 12,    -   M1, and M4 are each independently an arylene group represented        by Formulae 3a to 3j,    -   M2, and M3 are each independently a naphthalene group        represented by Formulae 3g to 3j,

-   -   wherein in Formulae 3a to 3j,    -   R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, and R₁₂ are each        independently hydrogen, a halogen, a hydroxy group, or a        substituted or unsubstituted C1-C10 alkyl group,    -   R_(c) and R_(d) are each independently a hydroxy group,    -   R_(e) is a halogen;    -   A1 is a substituted or unsubstituted C4-C12 alkylene group, a        substituted or unsubstituted C4-C12 alkenylene group, a        substituted or unsubstituted C4-C12 alkynylene group, a        substituted or unsubstituted C4-C12 alkadienylene group, or a        (poly)oxyalkylene group containing a substituted or        unsubstituted C1-C₅ alkylene group;    -   L1, L2, L3, and L4 are each independently —C(═O)—, —S(═O)—,        —C(═O)O—, —OC(═O)—, —S(═O)O—, —OS(═O)—, —O—C(═O)O—,        —(CH₂)₂—C(═O)—, —C(═O)—(CH₂)₂—, —C(═O)—CH═CH—, —CH═CH—C(═O)—,        —CH═N—, —N═CH—, —NH—C(═O)O—, —C(═O)—NH—, or —OC(═O)—NH—S(═O)O—,    -   E1, E2, and E are each independently an epoxy-containing group,    -   a1, a4, b1, and b2 each independently 0 or 1, and a2, and a3 are        each independently 1 or 2.

In Formula 1 and Formula 11, for example, L1, L2, L3, and L4 are eachindependently —C(═O)O— or —OC(═O)—.

When an epoxy compound is prepared using this method, an epoxy compoundmay be prepared at a high yield in a short period of time.

A first composition is provided by contacting a compound represented byFormula 11 with a compound represented by Formula 12.

For example, a compound represented by Formula 11 and a compoundrepresented by Formula 12 may be mixed in a reactor and provide a firstcomposition. For example, the compound represented by Formula 11 and thecompound represented by Formula 12 may be individually supplied to thereactor through different inlets. For example, the compound representedby Formula 11 and the compound represented by Formula 12 may each besupplied in a state dissolved in a solvent. Examples of the solvent arenot particularly limited, and any suitable solvent capable of dissolvingthe compound represented by Formula 11 and the compound represented byFormula 12 may be used as the solvent. The solvent may be omittedaccording to types of the reactants. For example, the compoundrepresented by Formula 11 and the compound represented by Formula 12 maybe mixed while continuously moving in the reactor. An example of thecompound represented by Formula 12 may be epichlorohydrin.

Also, a second composition including a compound represented by Formula 1may be prepared from the first composition.

For example, after mixing a compound having an aromatic ring and acompound having an epoxy-containing group in a reactor, the compoundincluding an aromatic ring and represented by Formula 1 may be producedby an acid catalyst or base catalyst reaction. In this regard, a secondcomposition including the compound may be prepared. An acid catalyst ora base catalyst used in the preparing of the second composition may bean organic catalyst instead of a metal catalyst. For example, an acidcatalyst or a base catalyst used in the preparing of the secondcomposition may be an organic acid catalyst or an organic base catalystnot including metal ions. The organic base catalyst may be, for example,tetrabutylammonium bromide (TBAB). The acid catalyst or base catalystmay be omitted according to types of the reactants.

The preparing of the second composition may be performed at atemperature of, for example, about 80° C. or higher, about 100° C. orhigher, about 120° C. or higher, about 140° C. or higher, about 160° C.or higher, or about 180° C. or higher. The preparing of the secondcomposition may be performed at a temperature, for example, in a rangeof about 80° C. to about 300° C., about 100° C. to about 290° C., about120° C. to about 280° C., about 140° C. to about 270° C., about 160° C.to about 260° C., or about 180° C. to about 250° C. In a conventional oravailable preparation method, performing the reaction at a temperatureof about 120° C. or higher was difficult, but the method according to anembodiment allows the reaction to be performed at a temperature of about120° C. or higher. As the reaction is performed at such a hightemperature, the reaction rate may be significantly increased, and thusthe reaction time may be significantly reduced as a result.

The preparing of the second composition may be performed at a pressureof, for example, about 1 atmosphere (atm) or higher, about 1.5 atm orhigher, about 2.0 atm or higher, about 2.5 atm or higher, about 3.0 atmor higher, about 3.5 atm or higher, about 4.0 atm or higher, about 4.5atm or higher, or about 5.0 atm or higher. The preparing of the secondcomposition may be performed at a pressure, for example, in a range ofabout 1 atm to about 20 atm, about 1.5 atm to about 20 atm, about 2.0atm to about 20 atm, about 2.5 atm to about 20 atm, about 3.0 atm toabout 20 atm, about 3.5 atm to about 20 atm, about 4.0 atm to about 20atm, about 4.5 atm to about 20 atm, or about 5.0 atm to about 20 atm. Asthe reaction is performed at such a high temperature, the reaction ratemay be significantly increased, and thus the reaction time may besignificantly reduced as a result.

The preparing of the second composition may be performed, for example,for about 60 minutes or less, about 50 minutes or less, about 40 minutesor less, about 30 minutes or less, about 20 minutes or less, or about 10minutes or less. The preparing of the second composition may beperformed, for example, for about 0.1 minutes to about 60 minutes, about0.1 minutes to about 50 minutes, about 0.5 minutes to about 40 minutes,about 1 minute to about 30 minutes, about 1 minute to about 20 minutes,or about 1 minute to about 10 minutes.

The first composition and the second composition may not include aprecipitate. When the first composition and the second composition donot include a precipitate, clogging of an inlet and/or an outlet of thereactor by the precipitate may be prevented. For example, the firstcomposition and the second composition may both be in a liquid phase.

In an embodiment, the second composition is recovered. A method ofrecovering the second composition is not particularly limited, and thesecond composition may be recovered from the reactor through an outletof the reactor. The outlet of the reactor is distinguished from theinlet of the reactor. For example, the inlet is located in a firstdirection of the reactor, and the outlet may be located in a seconddirection. For example, the second direction may be opposite from thefirst direction. An unreacted material and a solvent may be, forexample, removed from the recovered second composition, and a compoundrepresented by Formula 1 may be isolated.

Also, while the providing of the first composition is being performed,the recovering of the second composition may be performed. For example,the second composition represented by Formula 1 may be recovered throughthe outlet of the reactor while the compound represented by Formula 11and the compound represented by Formula 12 are being supplied to thereactor through the inlets of the reactor. As the recovering of thesecond composition is simultaneously performed while the providing ofthe first composition is being performed, the reaction time may bereduced, and the compound represented by Formula 1 may be obtained at ahigh yield.

A type of the reactor used in the preparation of the epoxy compound isnot particularly limited, and any suitable reactor in which therecovering of the second composition may be performed while theproviding of the first composition is being performed may be used as thereactor. The reactor may be, for example, a continuous reactor.

The method of preparing of an epoxy compound may further includepreparing the compound represented by Formula 11 by contacting acompound represented by Formula 13 with a base before the providing ofthe first composition:

R_(f)-(M1)_(a1)-(L1)_(b1)-(M2)_(a2)-L2-A1-L3-(M3)_(a3)-(L4)_(b2)-(M4)_(a4)-R_(g).  Formula13

In Formula 13,

-   -   M1, and M4 are each independently an arylene group represented        by Formulae 3a to 3j,    -   M2, and M3 are each independently a naphthalene group        represented by Formulae 3g to 3j,    -   A1 is a substituted or unsubstituted C4-C12 alkylene group, a        substituted or unsubstituted C4-C12 alkenylene group, a        substituted or unsubstituted C4-C12 alkynylene group, a        substituted or unsubstituted C4-C12 alkadienylene group, or a        (poly)oxyalkylene group containing a substituted or        unsubstituted C1-C5 alkylene group;    -   L1, L2, L3, and L4 are each independently —C(═O)O— or —OC(═O)—,    -   a1, a4, b1, and b2 are each independently 0 or 1, a2, and a3 are        each independently 1 or 2, and    -   R_(f) and R_(g) are each independently R_(h)C(═O)O—, wherein        R_(h) is an alkyl group of 1 to 5 carbon atoms. R_(h) may be,        for example, a methyl group. When R_(h) is a methyl group, the        reaction may further be facilitated.

The compound represented by Formula 11 may be prepared by contacting thecompound represented by Formula 13 with a base.

For example, the compound represented by Formula 13 and an organic basemay each be supplied in a state dissolved in a solvent. The solvent isnot particularly limited, and any suitable solvent capable of dissolvingthe compound represented by Formula 13 and an organic base may be usedas the solvent. The solvent may be omitted according to types of thereactants. For example, the compound represented by Formula 13 and anorganic base may be mixed while continuously moving in the reactor.

The base used in the preparation of a compound represented by Formula 11may be, for example, an organic base or an inorganic base. The inorganicbase may be, for example, a base including a metal cation. The organicbase used in the preparation of a compound represented by Formula 11 maybe, for example, a C1 to C10 alkyl amine. The organic base may be, forexample, a butyl amine. The inorganic base used in the preparation ofthe compound represented by Formula 11 may be, for example, NaOH or KOH.The organic base and/or inorganic base may be dissolved in an organicsolvent such as ethanol.

The acid catalyst or the base catalyst used in the preparation of thecompound represented by Formula 11 may be an organic catalyst instead ofa metal catalyst. For example, the acid catalyst or the base catalystused in the preparation of the compound having an aromatic ringrepresented by Formula 11 may be an organic acid catalyst or an organicbase catalyst not including metal ions. The organic base catalyst maybe, for example, a C1 to C10 alkyl amine. The organic base catalyst maybe, for example, a butyl amine. The acid catalyst or base catalyst maybe omitted according to types of the reactants.

The preparation of the compound represented by Formula 11 may beperformed at a temperature of, for example, about 20° C. or higher,about 40° C. or higher, about 60° C., about 80° C. or higher, about 100°C. or higher, about 120° C. or higher, about 140° C. or higher, about160° C. or higher, or about 180 or higher. The preparation of thecompound represented by Formula 11 may be performed at a temperature,for example, in a range of about 20° C. to about 300° C., about 40° C.to about 300° C., about 60° C. to about 300° C., about 80° C. to about300° C., about 100° C. to about 290° C., about 120° C. to about 280° C.,about 140° C. to about 270° C., about 160° C. to about 260° C., or about180° C. to about 250° C.

The preparation of the compound represented by Formula 11 may beperformed at a pressure of, for example, about 1 atm or higher, about1.5 atm or higher, about 2.0 atm or higher, about 2.5 atm or higher,about 3.0 atm or higher, about 3.5 atm or higher, about 4.0 atm orhigher, about 4.5 atm or higher, or about 5.0 atm or higher. Thepreparation of the compound represented by Formula 11 may be performedat a pressure, for example, in a range of about 1 atm to about 20 atm,about 1.5 atm to about 20 atm, about 2.0 atm to about 20 atm, about 2.5atm to about 20 atm, about 3.0 atm to about 20 atm, about 3.5 atm toabout 20 atm, about 4.0 atm to about 20 atm, about 4.5 atm to about 20atm, or about 5.0 atm to about 20 atm.

The preparation of the compound represented by Formula 11 may beperformed, for example, for about 60 minutes or less, about 50 minutesor less, about 40 minutes or less, about 30 minutes or less, about 20minutes or less, or about 10 minutes or less. The preparation of thecompound represented by Formula 11 may be performed, for example, forabout 0.1 minutes to about 60 minutes, about 0.1 minutes to about 50minutes, about 0.5 minutes to about 40 minutes, about 1 minute to about30 minutes, about 1 minute to about 20 minutes, or about 1 minute toabout 10 minutes.

The method of preparing an epoxy compound may further include preparinga compound represented by Formula 13 by contacting a compoundrepresented by Formula 14 with a compound represented by Formula 15before the preparing of the compound represented by Formula 11:

R_(i)-(M8)_(a8)-(L9)_(b5)-(M9)_(a9)-R_(j)  Formula 14

R_(k)-A1-R_(l).  Formula 15

In Formulae 14 and 15,

-   -   M8 is an arylene group represented by Formulae 3a to 3j,    -   M9 is a naphthalene group represented by Formulae 3g to 3j,    -   A1 is a substituted or unsubstituted C4-C12 alkylene group, a        substituted or unsubstituted C4-C12 alkenylene group, a        substituted or unsubstituted C4-C12 alkynylene group, a        substituted or unsubstituted C4-C12 alkadienylene group, or a        (poly)oxyalkylene group containing a substituted or        unsubstituted C1-C5 alkylene group;    -   L9 is —C(═O)O— or —OC(═O)—,    -   a8 and b5 are each independently 0 or 1, a9 is 1 or 2,    -   R_(i) is R_(m)C(═O)O—, wherein R_(m) is an alkyl group of 1 to 5        carbon atoms, and R_(j), R_(k), and R_(l) are each independently        a hydroxy group or a carboxyl group (—COOH).

The compound represented by Formula 14 may be represented by, forexample, one of Formulae 14a to 14d, and the compound represented byFormula 15 may be represented by, for example, one of Formulae 15a and15b:

R_(i)-(M8)-(L9)-(M9)_(a9)-COOH  Formula 14a

R_(i)-(M8)-(L9)-(M9)_(a9)-OH  Formula 14b

R_(i)-(M9)_(a9)-COOH  Formula 14c

R_(i)-(M9)_(a9)-OH  Formula 14d

HOOC-A1-COOH  Formula 15a

HO-A1-OH.  Formula 15b

In Formulae 14a to 14d, 15a, and 15b,

-   -   M8 is an arylene group represented by Formulae 3a to 3j,    -   M9 is a naphthalene group represented by Formulae 3g to 3j,    -   A1 is a substituted or unsubstituted C4-C12 alkylene group, a        substituted or unsubstituted C4-C12 alkenylene group, a        substituted or unsubstituted C4-C12 alkynylene group, a        substituted or unsubstituted C4-C12 alkadienylene group, or a        (poly)oxyalkylene group containing a substituted or        unsubstituted C1-C5 alkylene group;    -   L9 is —C(═O)O— or —OC(═O)—,    -   a9 is 1 or 2, and    -   R_(i) is R_(m)C(═O)O—, wherein R_(m) is an alkyl group of 1 to 5        carbon atoms.

The compound represented by Formula 13 may be prepared by contacting thecompound represented by Formula 14 with the compound represented byFormula 15.

For example, the compound represented by Formula 14 and the compoundrepresented by Formula 15 may each be supplied in a state dissolved in asolvent to the reactor. Examples of the solvent are not particularlylimited, and any suitable solvent capable of dissolving the compoundrepresented by Formula 13 and an organic base may be used as thesolvent. For example, the solvent may be a mixture solvent ofdichloromethane (MC) and dimethylformamide (DMF) or may bedimethylsulfoxide (DMSO). The solvent may be omitted according to typesof the reactants. For example, the compound represented by Formula 14and the compound represented by Formula 15 may be mixed whilecontinuously moving in the reactor.

An acid catalyst or a base catalyst used in the preparation of thecompound represented by Formula 13 may be an inorganic catalyst or anorganic catalyst. For synthesis by a high-speed continuous reaction orto suppress generation of metal ion impurities, an organic catalyst maybe used. For synthesis by a high-speed continuous reaction, a catalysthaving improved solubility in a reaction solution may be used. In thiscase, clogging of the reactor may be prevented in the synthesis by thehigh-speed continuous reaction flow.

For example, a catalyst used in the preparing of the compoundrepresented by Formula 13 may be an organic acid catalyst or an organicbase catalyst not including metal ions. An organic acid and an organicbase may be in the form of a salt to improve the solubility. The organicbase catalyst may be, for example, a complex of4-(dimethylamino)pyridine (DMAP) and p-toluenesulfonic acid (PTSA).

In a condensation reaction of preparing the compound represented byFormula 13, a carbodiimide compound, a 1-hydroxy-1,2,3-triazolederivative, a phosphonium-based compound, or a uronium-based compoundmay be used as a condensing agent. Since the solubility with respect toa reaction solution is improved for the synthesis by a high-speedcontinuous reaction, a condensing agent capable of suppressinggeneration of insoluble byproducts in the initial stage and untilcompletion of the reaction and performing the reaction without cloggingof the reactor in the middle of the synthesis by the high-speedcontinuous reaction flow may be used.

The condensing agent capable of suppressing generation of insolublebyproducts may be, for example, N,N′-diisopropylcarbodiimide (DIC) or1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC).Dicyclohexylcarbodiimide (DCC) produces a large amount of an insolublecompound and thus may interfere the progress of a high-speed continuousreaction.

The 1-hydroxy-1,2,3-triazole derivative may be, for example,1-hydroxybenzotriazole (HOBT) or 1-hydroxy-7-azabenzotriazole (HOAT).

The phosphonium-based condensing agent may be a compound such asbenzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate(PyBOP) or 7-azabenzotriazol-1-yloxy)tripyrrolidinophosphoniumhexafluorophosphate (PyAOP).

The uronium-based condensing agent may be, for example,hexafluorophosphate benzotriazole tetramethyl uronium (HBTU),hexafluorophosphate azabenzotriazole tetramethyl uronium (HATU),2-(1H-7-azabenzotriazole-1-yl)-1,1,3,3-tetramethyluroniumtetrafluoroborate (TATU), or2-(1H-benzotriazole-1-yl)-1,1,3,3-tetramethyluronium tetrafluoroborate(TBTU).

The condensing agents may be used alone or as a mixture of at least two.

The preparation of the compound represented by Formula 13 may beperformed at a temperature of, for example, about 20° C. or higher,about 40° C. or higher, about 60° C., about 80° C. or higher, about 100°C. or higher, about 120° C. or higher, about 140° C. or higher, about160° C. or higher, or about 180 or higher. The preparation of thecompound represented by Formula 13 may be performed at a temperature,for example, in a range of about 20° C. to about 300° C., about 40° C.to about 300° C., about 60° C. to about 300° C., about 80° C. to about300° C., about 100° C. to about 290° C., about 120° C. to about 280° C.,about 140° C. to about 270° C., about 160° C. to about 260° C., or about180° C. to about 250° C.

The preparation of the compound represented by Formula 13 may beperformed at a pressure of, for example, about 1 atm or higher, about1.5 atm or higher, about 2.0 atm or higher, about 2.5 atm or higher,about 3.0 atm or higher, about 3.5 atm or higher, about 4.0 atm orhigher, about 4.5 atm or higher, or about 5.0 atm or higher. Thepreparation of the compound represented by Formula 13 may be performedat a pressure, for example, in a range of about 1 atm to about 20 atm,about 1.5 atm to about 20 atm, about 2.0 atm to about 20 atm, about 2.5atm to about 20 atm, about 3.0 atm to about 20 atm, about 3.5 atm toabout 20 atm, about 4.0 atm to about 20 atm, about 4.5 atm to about 20atm, or about 5.0 atm to about 20 atm.

The preparation of the compound represented by Formula 13 may beperformed, for example, for about 60 minutes or less, about 50 minutesor less, about 40 minutes or less, about 30 minutes or less, about 20minutes or less, or about 10 minutes or less. The preparation of thecompound represented by Formula 13 may be performed, for example, forabout 0.1 minutes to about 60 minutes, about 0.1 minutes to about 50minutes, about 0.5 minutes to about 40 minutes, about 1 minute to about30 minutes, about 1 minute to about 20 minutes, or about 1 minute toabout 10 minutes.

In an embodiment, the method of preparing an epoxy compound may includepreparing a compound represented by Formula 13 by contacting a compoundrepresented by Formula 14 with a compound represented by Formula 15;preparing a compound represented by Formula 11 by contacting a compoundrepresented by Formula 13 with a base; preparing a first composition bycontacting the compound represented by Formula 11 with a compoundrepresented by Formula 12; preparing a second composition including acompound represented by Formula 1 from the first composition; andrecovering the second composition, wherein the recovering of the secondcomposition is performed while the preparing of the first composition isbeing performed. The method of preparing an epoxy compound may increasea reaction rate of a synthesis reaction and perform an isolation andpurification process as a continuous process without a separate processof isolation by precipitation in each synthesis step, and thus thesynthesis of an epoxy compound may be completed within about 24 hours,about 20 hours, about 16 hours, about 12 hours, about 8 hours, about 4hours, about 2 hours, or about 1 hour. The reaction may be performed ina microflow reactor.

A conventional or available method of preparing an epoxy compound usinga batch-type reactor such as a flask may have a low reaction rate andmay include a separate process of isolation by precipitation, which mayrequire, for example, about 80 hours or longer, about 90 hours orlonger, about 100 hours or longer, about 110 hours or longer, or about120 hours or longer to complete synthesis of the epoxy compound.

Hereinafter, definitions of substituents used in the formulae of thepresent specification are the same as follows.

As used herein, substituents of a substituted alkyl group, a substitutedalkylene group, a substituted alkenylene group, a substituted alkynylenegroup, and a substituted alkadienylene group may be each independently ahalogen atom, a hydroxyl group, a C1 to C5 alkyl group, a C1 to C5alkoxy group, or a combination thereof.

As used herein, the term “alkyl” refers to a fully saturated branched orunbranched (straight chain or linear) hydrocarbon group.

Example of the alkyl group are a methyl group, an ethyl group, ani-propyl group, an isopropyl group, an i-butyl group, an isobutyl group,a sec-butyl group, an i-pentyl group, an isopentyl group, a neopentylgroup, an i-hexyl group, a 3-methylhexyl group, a 2,2-dimethylpentylgroup, a 2,3-dimethylpentyl group, and an i-heptyl group.

At least one hydrogen atom of the alkyl group may be substituted with asubstituent a halogen atom, a hydroxyl group, an alkoxy group, a nitrogroup, a cyano group, an amino group, an amidino group, a hydrazine, ahydrazone, a carboxyl group, a carbamyl group, a thiol group, an estergroup, a carboxyl group or a salt thereof, a sulfonic acid group or asalt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkylgroup, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C30aryl group, a C7 to C30 arylalkyl group, a C1 to C30 alkoxy group, a C1to C5 alkylthio group, a C6-C30 aryloxy group, a C6-C30 arylthio group,a C1 to C20 heteroalkyl group, a C3 to C20 heterocyclo alkyl group, or acombination thereof.

As used herein, the term “alkenyl group” refers to an alkyl groupincluding at least one carbon-carbon double bond.

As used herein, the term “alkynyl group” refers to an alkyl groupincluding at least one carbon-carbon triple bond.

As used herein, the term “alkadienyl group” refers to an alkyl groupincluding two carbon-carbon double bonds.

Examples of “a halogen atom” include fluorine, bromine, chlorine, andiodine.

As used herein, the term “alkoxy” refers to “alkyl-O—,” where the alkylis the same as defined above. Examples of the alkoxy group may include amethoxy group, an ethoxy group, a propoxy group, a 2-propoxy group, abutoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group,a cyclopropoxy group, and a cyclohexyloxy group. At least one hydrogenatom in the alkoxy group may be substituted with the same substituent asdescribed above in connection with the alkyl group.

As used herein, the term “alkylthio” refers to “alkyl-S—,” where thealkyl is the same as defined above. Examples of the alkylthio group mayinclude a thiomethyl group, a thioethyl group, a thiopropyl group, a2-thiopropyl group, a thiobutyl group, a thio-tert-butyl group, athiopentyl group, a thiohexyl group, a thiocyclopropyl group, and athiocyclohexyl group. At least one hydrogen atom in the alkylthio groupmay be substituted with the same substituent as described above inconnection with the alkyl group.

As used herein, the term “aryl” is used alone or in combination, andrefers to an aromatic hydrocarbon group having one or more rings.

The term “aryloxy” used herein refers to aryl-O—, where the aryl is thesame as defined above. Non-limiting examples of the aryloxy group mayinclude a phenoxy group, a naphthoxy group, or a tetrahydronaphthyloxygroup. At least one hydrogen atom of the “aryloxy” group may besubstituted with the same substituent as described above in connectionwith the alkyl group.

The “arylthio” used herein refers to aryl-S—, where the aryl is the sameas defined above. Non-limiting examples of the arylthio group mayinclude a thiophenyl group, a thionaphthyl group, or athiotetrahydronaphthyl group. At least one hydrogen atom of the“arylthio” group may be substituted with the same substituent asdescribed above in connection with the alkyl group.

Also, as used herein, when a definition is not otherwise provided,‘hetero’ may refer to one including 1 to 4 heteroatoms I, O, S, Se, Te,Si, or P.

The term “aryl” also refers to a group in which an aromatic ring isfused to one or more cycloalkyl rings. Examples of the aryl group mayinclude a phenyl group, a naphthyl group, or a tetrahydronaphthyl group.At least one hydrogen atom of the aryl group may be substituted with thesame substituent as described above in connection with the alkyl group.

As used herein, the term “heteroaryl” refers to an aryl group, in whichat least one carbon atom or CH or CH₂ is substituted with a heteroatomor a chemical group containing at least one heteroatom.

As used herein, the term “alkylene group” refers to a bivalent aromatichydrocarbon group corresponding to an “alkyl” group.

As used herein, the term “alkenylene group” refers to a bivalentaromatic hydrocarbon group corresponding to an “alkenyl” group.

As used herein, the term “alkynylene group” refers to a bivalentaromatic hydrocarbon group corresponding to an “alkynyl” group.

As used herein, the term “alkadienylene group” refers to a bivalentaromatic hydrocarbon group corresponding to an “alkadienyl” group.

As used herein, the term “arylene group” refers to a bivalent aromatichydrocarbon group corresponding to an “aryl” group.

As used herein, the term “heteroarylene group” refers to a bivalent arylgroup in which at least one carbon atom or CH or CH₂ is substituted witha heteroatom or a chemical group containing at least one heteroatom.

As used herein, the open ended “—” refers to a bond or a methyl group,for example, in the following structures “—” without any R substituentrefers to a bond or a methyl group. For example,

The term “room temperature” used herein refers to a temperature of about25° C.

One or more embodiments will now be described in more detail withreference to the following examples. However, these examples are notintended to limit the scope of the one or more embodiments. The wording“‘B’ was used instead of ‘A”’ used in describing Synthesis Examplesmeans that an amount of ‘A’ used was identical to an amount of ‘B’ used,in terms of a molar equivalent.

EXAMPLES

Preparation of Epoxy Compound and Cured Product

Example 1 Preparation of Epoxy Compound

A solution prepared by completely dissolving 5 gram (g) (0.022 mole(mol)) of 6-acetoxy-2-naphthoic acid

and 0.35 g (0.0012 mol) of an organic salt catalyst(4-(dimethylamino)pyridinium 4-toluenesulfonate) formed of a complex ofDMAP/PTSA (4-dimethylaminopyridine/p-toluene sulfonic acid) in 35milliliter (ml) of a mixture solvent including methylene chloride (MC)and dimethylformamide (DMF) at a volume ratio of 60:40 was added to amicro reactor having a diameter of 1 millimeter (mm) through a firstinlet, and a mixture solution prepared by dissolving 1.30 g (0.011 mol)of 1,6-hexanediol, 1.52 g (0.024 mol) of N,N′-diisopropylcarbodiimide(DIC), and 3.27 g (0.024 mol) of 1-hydroxy-7-azabenzotriazole (HOAt) in35 ml of a mixture solvent of MC and DMF at a volume ratio of 60:40 wassimultaneously added to the reactor through a second inlet.

The solutions were mixed in the reactor and reacted, and thus

was produced as a result.

The temperature inside the reactor was about 25° C., and the reactiontime was about 1 hour. The production of the reaction was monitored bythe newly generated peak at 1722 cm⁻¹ by the In-line FT-IR.

In the reactor having the produced

20 ml of ethanol (EtOH) solution, in which 1.28 g (0.024 mol) ofpotassium hydroxide (KOH) was dissolved, was continuously added througha third inlet.

In the reactor, the solutions were mixed and reacted, and thus

was produced as a result.

The temperature inside the reactor was about 50° C., and the reactiontime was about 1 hour. The progression of the reaction was monitored bythe peak reduction at 1050 cm⁻¹ by the In-line FT-IR.

A HCl aqueous solution was added to the reactor including

through a fourth inlet to extract residual KOH, and a water (H₂O) layerwas removed using a liquid-water separator.

30 ml of methylethylketone (MEK), in which 0.135 g (0.4 millimole(mmol)) of tetrabutyl ammonium bromide (TBAB) and 19.5 g (0.21 mol) ofepichlorohydrin (ECH) were dissolved, was continuously added to theresidual solution through a fifth inlet.

The solutions were mixed and reacted in the reactor, and a compoundrepresented by Formula 9a was produced as a result. The temperatureinside the reactor was about 120° C., and the reaction time was about 10minutes.

While the compounds described above were continuously added to thereactor through the first, second, and third inlets of the reactor, acomposition including the compound represented by Formula 9a wascontinuously recovered through a first outlet of the reactor.

The solvent and unreacted materials were isolated and purified from therecovered composition, and thus a compound represented by Formula 9a wasobtained.

A molecular weight (m/z=571.23) of the compound was confirmed by aliquid chromatography mass spectrometry (LC-MS).

A molecular structure of the compound represented by Formula 9a wasconfirmed by proton nuclear magnetic resonance (¹H-NMR). ¹H NMR(DMSO-d6, δ ppm): 1.50 (2H), 1.77 (2H), 2.75 (1H), 2.83 (1H), 3.41 (1H),4.0 (1H) 4.31 (2H), 4.5 (1H) 7.30 (1H), 7.45 (1H), 7.80 (1H), 7.92 (1H),8.04 (1H), 8.52 (1H).

A melting point of the compound represented by Formula 9a measured by adynamic scanning calorimetry (DSC) was about 171° C.

The reaction may be represented by, for example, the flowchart shown inFIG. 6.

Preparation of Cured Product

The prepared epoxy compound represented by Formula 9a and a phenol-basedcuring agent, MEH7500 (a multifunctional phenol available from MeiwaPlastic Industries, LTD), were mixed at an equivalent ratio of 1:1 toprepare an epoxy resin composition.

5 g of the prepared epoxy resin composition was added to an aluminummold and cured by heating the mold to 190° C. to prepare a cured productof the epoxy resin composition as a sample.

Example 2 Preparation of Epoxy Compound

An epoxy compound represented by Formula 9b was synthesized in the samemanner as in Example 1 under the same conditions, except that 1.15 g(0.011 mol) of 1,5-pentanediol was used instead of hexanediol.

A molecular weight (m/z=557.22) of the compound was confirmed by LC-MS.

A molecular structure of the compound represented by Formula 9b wasconfirmed by ¹H-NMR. ¹H NMR (DMSO-d6, δ ppm): 1.61 (1H), 1.77 (2H), 2.77(1H), 2.85 (1H), 3.41 (1H), 4.0 (1H) 4.31 (2H), 4.5 (1H) 7.25 (1H), 7.38(1H), 7.80 (1H), 7.92 (1H), 7.98 (1H), 8.52 (1H).

A melting point of the compound represented by Formula 9b measured byDSC was about 96° C.

Preparation of Cured Product

The prepared epoxy compound represented by Formula 9b and a phenol-basedcuring agent, MEH7500 (a multifunctional phenol available from MeiwaPlastic Industries, LTD), were mixed at an equivalent ratio of 1:1 toprepare an epoxy resin composition.

5 g of the prepared epoxy resin composition was added to an aluminummold and cured by heating the mold to 190° C. to prepare a cured productof the epoxy resin composition as a sample.

Example 3 Preparation of Epoxy Compound

An epoxy compound represented by Formula 9c was synthesized in the samemanner as in Example 1 under the same conditions, except that 0.99 g(0.011 mol) of 1,4-butanediol was used instead of hexanediol.

A molecular weight (m/z=543.20) of the compound represented by Formula9c was confirmed by LC-MS.

A molecular structure of the compound represented by Formula 9c wasconfirmed by ¹H-NMR. ¹H NMR (DMSO-d6, δ ppm): 1.95 (2H), 2.78 (1H), 2.90(1H), 3.43 (1H), 4.0 (1H) 4.43 (2H), 4.5 (1H), 7.29 (1H), 7.43 (1H),7.87 (1H), 7.95 (1H), 8.05 (1H), 8.56 (1H).

A melting point of the compound represented by Formula 9c measured byDSC was about 126° C.

Preparation of Cured Product

The prepared epoxy compound represented by Formula 9c and a phenol-basedcuring agent, MEH7500 (a multifunctional phenol available from MeiwaPlastic Industries, LTD), were mixed at an equivalent ratio of 1:1 toprepare an epoxy resin composition.

5 g of the prepared epoxy resin composition was added to an aluminummold and cured by heating the mold to 190° C. to prepare a cured productof the epoxy resin composition as a sample.

Example 4 Preparation of Epoxy Compound

completely dissolved in 70 ml of a mixture solvent including MC and DMFat a volume ratio of 60:40 was synthesized in the same manner as inExample 2, except that 1.15 g (0.011 mol) of 1,5-pentanediol was usedinstead of hexanediol.

1.52 g (0.024 mol) of N,N′-diisopropylcarbodiimide (DIC), 3.27 g (0.024mol) of 1-hydroxy-7-azabenzotriazole, and 3.96 g (0.022 mol) ofacetoxybenzoic acid completely dissolved in a mixture of MC and DMF at avolume ratio of 60:40 and 0.35 g (0.0012 mol) of an organic saltcatalyst formed of a complex of DMAP/PTSA were added to a micro reactorhaving a diameter of 1 mm through a fifth inlet, and these were reactedto produce

The temperature inside the reactor was about 25° C., and the reactiontime was about 1 hour.

In the reactor having the produced

20 ml of EtOH solution, in which 1.28 g (0.024 mol) of KOH wasdissolved, was continuously added through a sixth inlet.

In the reactor, the solutions were mixed and reacted, and thus

was produced as a result. The temperature inside the reactor was about25° C., and the reaction time was about 2 hours.

A HCl aqueous solution was added to the reactor including

through a seventh inlet to extract residual KOH, and a water (H₂O) layerwas removed using a liquid-water separator.

19.5 g (0.21 mol) epichlorohydrin (ECH) dissolved in 0.135 g (0.4 mmol)of tetrabutyl ammonium bromide (TBAB) was continuously added to thereactor through an eighth inlet.

The solutions were mixed and reacted in the reactor, and a compoundrepresented by Formula 9f was produced as a result. The temperatureinside the reactor was about 110° C., and the reaction time was about 30minutes.

The solvent and unreacted materials were separated and purified from therecovered composition, and thus a compound represented by Formula 9f wasobtained.

A molecular weight (m/z=797.42) of the compound represented by Formula9f was confirmed by LC-MS.

A molecular structure of the compound represented by Formula 9f wasconfirmed by ¹H-NMR. ¹H NMR (DMSO-d6, δ ppm): 1.61 (1H), 1.77 (2H), 2.77(1H), 2.85 (1H), 3.41 (1H), 4.0 (1H) 4.31 (2H), 4.5 (1H) 7.25 (1H), 7.38(1H), 7.80 (1H), 7.85 (2H), 7.92 (1H), 7.98 (1H), 8.06 (2H), 8.52 (1H).

A melting point of the compound represented by Formula 9f measured byDSC was about 72.6° C.

Preparation of Cured Product

The prepared epoxy compound represented by Formula 9f and a phenol-basedcuring agent, MEH7500 (a multifunctional phenol available from MeiwaPlastic Industries, LTD), were mixed at an equivalent ratio of 1:1 toprepare an epoxy resin composition.

5 g of the prepared epoxy resin composition was added to an aluminummold and cured by heating the mold to 190° C. to prepare a cured productof the epoxy resin composition as a sample.

Example 5 Preparation of Epoxy Compound

11.71 g of 4-acetoxybenzoic acid completely dissolved in 90 ml of amixture solvent including MC and DMF at a volume ratio of 80:20 and 1 g(0.0034 mol) of an organic salt catalyst formed of a complex ofDMAP/PTSA were added to a micro reactor having a diameter of 1 mmthrough a first inlet, and a mixture solution prepared by dissolving 5 g(0.031 mol) of 2,6-dihydroxynaphthalene, 6.3 g (0.1 mol) ofN,N′-diisopropylcarbodiimide (DIC), and 6.81 g (0.05 mol) of1-hydroxy-7-azabenzotriazole (HOAt) in 90 ml of a mixture of MC and DMFat a volume ratio of 80:20 was simultaneously added to the reactorthrough a second inlet.

The solutions were mixed in the reactor and reacted, and thus

was produced as a result. The temperature inside the reactor was about25° C., and the reaction time was about 1 hour.

In the reactor having the produced

50 ml of EtOH solution, in which 3.65 g (0.065 mol) of KOH wasdissolved, was continuously added through a third inlet.

In the reactor, the solutions were mixed and reacted, and thus

was produced as a result. The temperature inside the reactor was about50° C., and the reaction time was about 1 hour.

A HCl aqueous solution was added to the reactor including

through a fourth inlet to extract residual KOH, and a water (H₂O) layerwas removed using a liquid-water separator.

1 g (0.0034 mol) of an organic salt catalyst formed of a complex ofDMAP/PTSA was added to a micro reactor having a diameter of 1 mm througha fifth inlet, and a mixture solution prepared by dissolving 7.42 g(0.065 mol) of 5-hexenoic acid, 6.3 g (0.1 mol) ofN,N′-diisopropylcarbodiimide (DIC), and 6.54 g (0.048 mol) of1-hydroxy-7-azabenzotriazole in 90 ml of a mixture including MC and DMFat a volume ratio of 80:20 was simultaneously added to the reactorthrough a sixth inlet.

In the reactor, the solutions were mixed and reacted, and thus

was produced as a result. The temperature inside the reactor was about25° C., and the reaction time was about 1 hour.

A composition including the compound

was recovered into a flask, the solvent was removed by vacuumdistillation, the product was precipitated in methanol, and theprecipitate was separated and dried.

7.4 g (0.0125 mol) of the dried product compound was added to a 250 mlflask and dissolved in 70 ml of methylene chloride (MC), and 7.3 g(0.042 mol) of m-chloroperoxybenzoic acid (MCPBA), 15 g (0.128 mol) ofN-methylmorpholine N-oxide (NMO), and 0.565 g (0.001 mol) of a Mn Salencomplex of the formula

were added and allowed to react at room temperature for 1 hour.

The precipitate produced after completion of the reaction was removed bya filter, the solvent and unreacted materials were isolated and purifiedfrom the recovered composition, and thus a compound represented byFormula 10b was obtained.

A molecular weight (m/z=625.2) of the compound represented by Formula10b was confirmed by LC-MS.

A molecular structure of the compound represented by Formula 10b wasconfirmed by 1H-NMR. 1H NMR (DMSO-d6, δ ppm): 1.50 (1H), 1.62 (1H), 1.77(2H), 2.44 (1H), 2.70 (3H), 2.91 (1H), 7.35 (2H), 7.51 (1H), 7.89 (1H),8.02 (1H), 8.21 (2H).

A melting point of the compound represented by Formula 10b measured byDSC was about 138° C.

Preparation of Cured Product

The prepared epoxy compound represented by Formula 10b and aphenol-based curing agent, MEH7500 (a multifunctional phenol availablefrom Meiwa Plastic Industries, LTD), were mixed at an equivalent ratioof 1:1 to prepare an epoxy resin composition.

5 g of the prepared epoxy resin composition was added to an aluminummold and cured by heating the mold to 190° C. to prepare a cured productof the epoxy resin composition as a sample.

Example 6 Preparation of Epoxy Compound

An epoxy compound represented by Formula 10f was synthesized in the samemanner as in Example 5 under the same conditions, except that 5 g (0.031mol) of 2,7-dihydroxynaphthalene was used instead of 5 g (0.031 mol) of2,6-dihydroxynaphthalene.

A molecular weight (m/z=625.2) of the compound represented by Formula10f was confirmed by LC-MS.

A molecular structure of the compound represented by Formula 10f wasconfirmed by ¹H-NMR. ¹H NMR (DMSO-d6, δ ppm): 1.50 (1H), 1.62 (1H), 1.77(2H), 2.44 (1H), 2.70 (3H), 2.91 (1H), 7.40 (2H), 7.51 (1H), 7.89 (1H),8.11 (1H), 8.25 (2H).

A melting point of the compound represented by Formula 10f measured byDSC was about 129° C.

Preparation of Cured Product

The prepared epoxy compound represented by Formula 10f and aphenol-based curing agent, MEH7500 (a multifunctional phenol availablefrom Meiwa Plastic Industries, LTD), were mixed at an equivalent ratioof 1:1 to prepare an epoxy resin composition.

5 g of the prepared epoxy resin composition was added to an aluminummold and cured by heating the mold to 190° C. to prepare a cured productof the epoxy resin composition as a sample.

Example 7 Preparation of Epoxy Compound

An epoxy compound represented by Formula 10a was synthesized in the samemanner as in Example 5 under the same conditions, except that 6.54 g(0.065 mol) of 4-pentenoic acid was used instead of 7.42 g (0.065 mol)of 5-hexenoic acid.

A molecular weight (m/z=597.17) of the compound represented by Formula10a was confirmed by LC-MS.

A molecular structure of the compound represented by Formula 10a wasconfirmed by ¹H-NMR. ¹H NMR (DMSO-d6, δ ppm): 1.78 (1H), 1.94 (1H), 2.45(1H), 2.70 (3H), 2.91 (1H), 7.38 (2H), 7.51 (1H), 7.89 (1H), 8.01 (1H),8.21 (2H).

A melting point of the compound represented by Formula 10a measured byDSC was about 183° C.

Preparation of Cured Product

The prepared epoxy compound represented by Formula 10a and aphenol-based curing agent, MEH7500 (a multifunctional phenol availablefrom Meiwa Plastic Industries, LTD), were mixed at an equivalent ratioof 1:1 to prepare an epoxy resin composition.

5 g of the prepared epoxy resin composition was added to an aluminummold and cured by heating the mold to 190° C. to prepare a cured productof the epoxy resin composition as a sample.

Example 8 Preparation of Epoxy Compound

In a 3-neck glass flask of 250 ml, 5 g (0.022 mol) of 4-acetoxynaphthoic acid

0.37 g (0.003 mol) of a DMAP catalyst, and 1.30 g (0.011 mol) of1,6-hexanediol were completely dissolved in 70 ml of methylene chloride(MC), and 1.52 g (0.024 mol) of N,N′-diisopropylcarbodiimide (DIC) wasadded dropwise over 5 minutes.

In the reactor, the solutions were mixed and reacted, and thus

was produced as a result. The temperature inside the reactor was about25° C., and the appropriate reaction time was about 16 hours.

MC in the reactor in which

was produced was removed using a rotary vacuum distiller, and theresultant was dried for 16 hours.

After the drying process, the resultant was dissolved in 50 ml of asolvent including toluene and THF at a volume ratio of 50:50 in a flaskof 100 ml, and 20 ml of an ethanol (EtOH) solution, in which 1.28 g(0.024 mol) of KOH was dissolved, was added thereto. Thus, the solutionswere mixed and reacted, and thus

(MW=458.1) was produced as a result. The temperature inside the reactorwas about 50° C., and the reaction time was about 2 hours.

A HCl aqueous solution was added to the reactor including

through a fourth inlet to extract residual KOH, and a water (H₂O) layerwas removed using a liquid-water separator.

The solvent in the residual solution was removed using a rotary vacuumdistiller, the product was precipitated in methanol, and the precipitatewas separated using a filter and vacuum dried at 60° C. for 16 hours.

The dried product was added to 30 ml of methylethylketone (MEK), inwhich 0.135 g (0.4 mmol) of tetrabutyl ammonium bromide (TBAB) and 19.5g (0.21 mol) of epichlorohydrin (ECH) were dissolved, in a 3-neck flaskof 250 ml to be reacted. The temperature inside the reactor was about80° C., and the reaction time was about 6 hours.

When the reaction temperature was higher than 80° C., byproducts such asdimers were generated in excess.

The solvent and unreacted materials were isolated and purified from therecovered composition, and thus a compound represented by Formula 9a wasobtained.

A molecular weight (m/z=571.23) of the compound represented by Formula9a was confirmed by LC-MS.

A molecular structure of the compound represented by Formula 9a wasconfirmed by ¹H-NMR. ¹H NMR (DMSO-d6, δ ppm): 1.50 (2H), 1.77 (2H), 2.75(1H), 2.83 (1H), 3.41 (1H), 4.0 (1H) 4.31 (2H), 4.5 (1H) 7.30 (1H), 7.45(1H), 7.80 (1H), 7.92 (1H), 8.04 (1H), 8.52 (1H).

A melting point of the compound represented by Formula 9a measured byDSC was about 171° C.

Comparative Example 1 Preparation of Epoxy Compound

An epoxy compound represented by Formula A was synthesized in the samemanner as in Example 1 under the same conditions, except that 3.91 g(0.022 mol) of 4-acetoxybenzoicacid was used instead of6-acetoxy-2-naphthoic acid.

A molecular weight (m/z=471.23) of the compound represented by Formula Awas confirmed by LC-MS.

A molecular structure of the compound represented by Formula A wasconfirmed by ¹H-NMR. ¹H NMR (DMSO-d6, δ ppm): 1.45 (2H), 1.78 (2H), 2.75(1H), 2.83 (1H), 3.41 (1H), 4.0 (1H) 4.31 (2H), 4.5 (1H) 7.03 (2H), 7.92(2H).

A melting point of the compound represented by Formula A was notmeasured by DSC.

Preparation of Cured Product

The prepared epoxy compound represented by Formula A and a phenol-basedcuring agent, MEH7500 (a multifunctional phenol available from MeiwaPlastic Industries, LTD), were mixed at an equivalent ratio of 1:1 toprepare an epoxy resin composition.

5 g of the prepared epoxy resin composition was added to an aluminummold and cured by heating the mold to 190° C. to prepare a cured productof the epoxy resin composition as a sample.

Comparative Example 2 Preparation of Epoxy Compound

An epoxy compound represented by Formula B was synthesized in the samemanner as in Example 1 under the same conditions, except that 5.64 g(0.022 mol) of 4′-acetoxy-biphenyl-4-carboxylic acid was used instead of6-acetoxy-2-naphthoic acid and 0.99 g (0.011 mol) of 1,4-butanediol wasused instead of hexanediol.

A molecular weight (m/z=595.23) of the compound represented by Formula Bwas confirmed by LC-MS.

A molecular structure of the compound represented by Formula B wasconfirmed by ¹H-NMR. ¹H NMR (DMSO-d6, δ ppm): 1.98 (2H), 2.79 (1H), 2.93(1H), 3.40 (1H), 4.0 (1H) 4.30 (1H), 4.44 (2H) 7.01 (2H), 7.55 (2H),7.62 (2H), 8.08 (2H).

A melting point of the compound represented by Formula B measured by DSCwas about 212° C.

Preparation of Cured Product

The prepared epoxy compound represented by Formula B and a phenol-basedcuring agent, MEH7500 (a multifunctional phenol available from MeiwaPlastic Industries, LTD), were mixed at an equivalent ratio of 1:1 toprepare an epoxy resin composition.

5 g of the prepared epoxy resin composition was added to an aluminummold and cured by heating the mold to 190° C. to prepare a cured productof the epoxy resin composition as a sample.

Evaluation Example 1: Measurement of Reaction Time

The time and yield required to prepare the epoxy compounds of Examples 1to 8 were measured. The results of the measurement are shown in Table 1.

The time required for the preparation evaluated as the time required toprepare the epoxy compounds of the same amount (for example, the samenumber of moles) from the time the reactant was added.

TABLE 1 Reaction time Synthesis yield [Minute] [%] Example 1 Less than 6hours 42% Example 2 Less than 6 hours 38% Example 3 Less than 6 hours45% Example 4 Less than 9 hours 33% Example 5 Less than 8 hours 40%Example 6 Less than 8 hours 38% Example 7 Less than 8 hours 35% Example8 4 days 45%

As shown in Table 1, the time required to prepare the epoxy compound inthe continuous reactor of Examples 1 to 7 was reduced to about 25% orless of the time required to prepare the epoxy compound in the batchreactor of Example 8.

Evaluation Example 2: Measurement of Thermal Conductivity and MeltingPoint

The thermal conductivities of samples, which are the cured products ofthe epoxy resin compositions including the epoxy compounds and a curingagent prepared in Examples 1 to 5 and Comparative Examples 1 to 4, weremeasured. The results of the measurement are shown in Table 2.

Melting points of the epoxy compounds prepared in Examples 1 to 5 andComparative Examples 1 to 4 were measured.

The thermal conductivities were evaluated by a modified transient planesource (MTPS) technique using a C-THERM TCI™ thermal conductivityanalyzer.

A DSC peak temperature measured in a dynamic scanning calorimeter (DSC)by increasing a temperature at a rate of 10 degrees per minute was usedas the melting temperature. The DSC peak temperature was the meltingtemperature of the epoxy compound.

TABLE 2 Thermal conductivity [W/mk] Example 1 0.34 Example 2 0.33Example 3 0.34 Example 4 0.30 Example 5 0.30 Example 6 0.31 Example 70.31 Comparative Example 1 0.21 Comparative Example 2 0.34

As shown in Table 2, the cured products obtained from the epoxycompounds of Examples 1 to 7 had improved thermal conductivities ascompared with that of the cured product obtained from the epoxy compoundof Comparative Example 1.

Also, melting temperatures of the epoxy compounds of Examples 1 to 7were all about 200° C. or lower. On the other hand, a meltingtemperature of the epoxy compound of Comparative Example 2 was about212° C., which was inappropriate for an epoxy molding condition.

According to an aspect of an embodiment, when an epoxy resin compositionincludes an epoxy compound having an aromatic ring, thermal conductivityof a cured product of the epoxy resin composition is improved, thermalstability of a semiconductor device, an electronic device, and anarticle including the cured product may be improved, and a time forsynthesizing an epoxy compound having an aromatic ring may be reduced.

It should be understood that embodiments described herein should beconsidered in a descriptive sense only and not for purposes oflimitation. Descriptions of features or aspects within each embodimentshould typically be considered as available for other similar featuresor aspects in other embodiments. While one or more embodiments have beendescribed with reference to the figures, it will be understood by thoseof ordinary skill in the art that various changes in form and detailsmay be made therein without departing from the spirit and scope of thepresent detailed description as defined by the following claims.

What is claimed is:
 1. An epoxy compound including an aromatic ringrepresented by Formula 1 or Formula 2:E1-(M1)_(a1)-(L1)_(b1)-(M2)_(a2)-L2-A1-L3-(M3)_(a3)-(L4)_(b2)-(M4)_(a4)-E2  Formula1E3-(A2)_(c1)-(L5)_(b3)-(M5)_(a5)-L6-(M6)_(a6)-L7-(M7)_(a7)-(L8)_(b4)-(A3)_(c2)-E4,  Formula2 wherein, in Formulae 1 and 2, M1, M4, M5, and M7 are eachindependently an arylene group represented by Formulae 3a to 3j, M2, M3,and M6 are each independently a naphthalene group represented byFormulae 3g to 3j,

 wherein, in Formulae 3a to 3j,  R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉,R₁₀, R₁₁, and R₁₂ are each independently a hydrogen, a halogen, ahydroxy group, or a substituted or unsubstituted C1-C10 alkyl group; A1,A2, and A3 are each independently a substituted or unsubstituted C4-C12alkylene group, a substituted or unsubstituted C4-C12 alkenylene group,a substituted or unsubstituted C4-C12 alkynylene group, a substituted orunsubstituted C4-C12 alkadienylene group, or a (poly)oxyalkylene groupcomprising a substituted or unsubstituted C1-C5 alkylene group; L1, L2,L3, L4, L5, L6, L7, and L8 are each independently —C(═O)O— or —OC(═O)—,E1, E2, E3, and E4 are each independently an epoxy-containing group, a1,a4, b1, b2, b3, b4, c1, and c2 are each independently 0 or 1, and a2,a3, a5, a6 and a7 are each independently 1 or
 2. 2. The epoxy compoundof claim 1, wherein the epoxy compound having an aromatic ringrepresented by Formula 1 is an epoxy compound having an aromatic ringrepresented by one of Formulae 4a to 4f:E1-M2-L2-A1-L3-M3-E2  Formula 4aE1-M1-L1-M2-L2-A1-L3-M3-E2  Formula 4bE1-M2-L2-A1-L3-M3-L4-M4-E2  Formula 4cE1-M1-L1-M2-L2-A1-L3-M3-L4-M4-E2  Formula 4dE1-M1-M2-L2-A1-L3-M3-L4-M4-E2  Formula 4eE1-M1-L1-M2-L2-A1-L3-M3-M4-E2  Formula 4f wherein, in Formulae 4a to 4f,M1 and M4 are each independently an arylene group represented byFormulae 3a to 3j, M2 and M3 are each independently a naphthalene grouprepresented by Formulae 4a to 4d, A1 is a substituted or unsubstitutedC4-C12 alkylene group, a substituted or unsubstituted C4-C12 alkenylenegroup, a substituted or unsubstituted C4-C12 alkynylene group, asubstituted or unsubstituted C4-C12 alkadienylene group, or a(poly)oxyalkylene group comprising a substituted or unsubstituted C1-05alkylene group; L1, L2, L3, and L4 are each independently —C(═O)O— or—OC(═O)—, and E1, E2, E3, and E4 are each independently anepoxy-containing group.
 3. The epoxy compound of claim 1, wherein theepoxy compound having an aromatic ring represented by Formula 2 is anepoxy compound represented by one of Formulae 5a to 5e:E3-A2-L5-M5-L6-M6-L7-M7-L8-A3-E4  Formula 5aE3-M5-L6-M6-L7-M7-L8-A3-E4  Formula 5bE3-A2-L5-M5-L6-M6-L7-M7-E4  Formula 5cE3-A2-L6-M6-L7-M7-L8-A3-E4  Formula 5dE3-A2-L5-M5-L6-M6-L7-A3-E4  Formula 5e wherein, in Formulae 5a to 5e, M5and M7 are each independently an arylene group represented by Formulae3a to 3j, M6 is a naphthalene group represented by Formulae 4a to 4d, A2and A3 are each independently a substituted or unsubstituted C4-C12alkylene group, a substituted or unsubstituted C4-C12 alkenylene group,a substituted or unsubstituted C4-C12 alkynylene group, a substituted orunsubstituted C4-C12 alkadienylene group, or a (poly)oxyalkylene groupcomprising a substituted or unsubstituted C1-C5 alkylene group; L5, L6,L7, and L8 are each independently —C(═O)O— or —OC(═O)—, and E1, E2, E3,and E4 are each independently an epoxy-containing group.
 4. The epoxycompound of claim 1, wherein A1, A2, and A3 are each independently anethylene group, a propylene group, a butylene group, a pentylene group,a hexylene group, a heptylene group, an octylene group, a nonylenegroup, a decylene group, an undecylene group, a dodecylene group, abutadienylene group, a pentadienylene group, a hexadienylene group, aheptadienylene group, an octadienylene group, a nonadienylene group, adecadienylene group, an undecadienylene group, a dodecadienylene group,or —(CH₂O)p- (where p is a real number of 1 to 10), and L1, L2, L3, L4,L5, L6, L7, and L8 are each independently —C(═O)O— or —OC(═O)—.
 5. Theepoxy compound of claim 1, wherein E1 and E2 are each independently anepoxy-containing group represented by Formulae 6a to 6f:

wherein, in Formulae 6a to 6f, R_(a), and R_(b) are each independently ahydrogen, a halogen, a hydroxy group, or a substituted or unsubstitutedC1-C10 alkyl group, n1 is 2 to 10, and n2 is 1 to
 10. 6. The epoxycompound of claim 1, wherein M1, M4, M5, and M7 are each independentlyan arylene group represented by Formula 7a to 7j, M2, M3, and M6 areeach independently a naphthalene group represented by Formula 7g to 7j,and E1 and E2 are each independently an epoxy-containing grouprepresented by Formulae 8a to 8f:

wherein, in Formulae 8a to 8f, n1 is 1 to 10, and n2 is 2 to
 10. 7. Theepoxy compound of claim 1, wherein the epoxy compound represented byFormula 1 is represented by one of Formulae 9a to 9p:


8. The epoxy compound of claim 1, wherein the epoxy compound representedby Formula 2 is represented by one of


9. The epoxy compound of claim 1, wherein a melting point of the epoxycompound represented by Formula 1 or Formula 2 is about 200° C. orlower.
 10. An epoxy resin composition comprising: the epoxy compound ofclaim 1; and a curing agent.
 11. The epoxy resin composition of claim10, wherein a metal ion content of the resin composition is about 10parts per million or less.
 12. The epoxy resin composition of claim 10further comprising a filler, wherein the filler is an inorganic filler,an organic filler, or a combination thereof.
 13. The epoxy resincomposition of claim 12, wherein an amount of the filler is in a rangeof about 20 weight % to about 99 weight % based on the total weight ofthe epoxy resin composition.
 14. A semiconductor device comprising asubstrate; a semiconductor; and a cured product of an epoxy resincomposition comprising a curing agent, and an epoxy compound representedby Formula 1, an epoxy compound represented by Formula 2, or acombination thereof, a sealing portion comprising the cured product ofthe epoxy resin composition, a substrate portion comprising the curedproduct of the epoxy resin composition, a reinforcement portioncomprising the cured product of the epoxy resin composition, or anadhesive portion comprising the cured product of the epoxy resincomposition:E1-(M1)_(a1)-(L1)_(b1)-(M2)_(a2)-L2-A1-L3-(M3)_(a3)-(L4)_(b2)-(M4)_(a4)-E2  Formula1E3-(A2)_(c1)-(L5)_(b3)-(M5)_(a5)-L6-(M6)_(a6)-L7-(M7)_(a7)-(L8)_(b4)-(A3)_(c2)-E4  Formula2 wherein, in Formulae 1 and 2, M1, M4, M5, and M7 are eachindependently an arylene group represented by Formulae 3a to 3j, M2, M3,and M6 are each independently a naphthalene group represented byFormulae 3g to 3j,

 wherein, in Formulae 3a to 3j,  R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉,R₁₀, R₁₁, and R₁₂ are each independently a hydrogen, a halogen, ahydroxy group, or a substituted or unsubstituted C1-C10 alkyl group; A1,A2, and A3 are each independently a substituted or unsubstituted C4-C12alkylene group, a substituted or unsubstituted C4-C12 alkenylene group,a substituted or unsubstituted C4-C12 alkynylene group, a substituted orunsubstituted C4-C12 alkadienylene group, or a (poly)oxyalkylene groupcomprising a substituted or unsubstituted C1-C5 alkylene group; L1, L2,L3, L4, L5, L6, L7, and L8 are each independently —C(═O)O— or —OC(═O)—,E1, E2, E3, and E4 are each independently an epoxy-containing group, a1,a4, b1, b2, b3, b4, c1, and c2 are each independently 0 or 1, and a2,a3, a5, a6, and a7 are each independently 1 or
 2. 15. The semiconductordevice of claim 14, wherein a thermal conductivity of the cured productsof the epoxy resin compositions is about 0.25 Watts per meter-Kelvin ormore.
 16. An electronic device comprising: a substrate; an electroniccomponent; and a cured product of an epoxy resin composition comprisinga curing agent, and an epoxy compound represented by Formula 1, an epoxycompound represented by Formula 2, or a combination thereof, a sealingportion comprising the cured product of the epoxy resin composition, asubstrate portion comprising the cured product of the epoxy resincomposition, a reinforcement portion comprising the cured product of theepoxy resin composition, or an adhesive portion comprising the curedproduct of the epoxy resin composition:E1-(M1)_(a1)-(L1)_(b1)-(M2)_(a2)-L2-A1-L3-(M3)_(a3)-(L4)_(b2)-(M4)_(a4)-E2  Formula1E3-(A2)_(c1)-(L5)_(b3)-(M5)_(a5)-L6-(M6)_(a6)-L7-(M7)_(a7)-(L8)_(b4)-(A3)_(c2)-E4  Formula2 wherein, in Formulae 1 and 2, M1, M4, M5, and M7 are eachindependently an arylene group represented by Formulae 3a to 3j, M2, M3,and M6 are each independently a naphthalene group represented byFormulae 3g to 3j,

 wherein, in Formulae 3a to 3j,  R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉,R₁₀, R₁₁, and R₁₂ are each independently a hydrogen, a halogen, ahydroxy group, or a substituted or unsubstituted C1-C10 alkyl group; A1,A2, and A3 are each independently a substituted or unsubstituted C4-C12alkylene group, a substituted or unsubstituted C4-C12 alkenylene group,a substituted or unsubstituted C4-C12 alkynylene group, a substituted orunsubstituted C4-C12 alkadienylene group, or a (poly)oxyalkylene groupcomprising a substituted or unsubstituted C1-C5 alkylene group; L1, L2,L3, L4, L5, L6, L7, and L8 are each independently —C(═O)O— or —OC(═O)—,E1, E2, E3, and E4 are each independently an epoxy-containing group, a1,a4, b1, b2, b3, b4, c1, and c2 are each independently 0 or 1, and a2,a3, a5, a6, and a7 are each independently 1 or
 2. 17. The electronicdevice of claim 16, wherein a thermal conductivity of the cured productsof the epoxy resin compositions is about 0.25 Watts per meter-Kelvin ormore.
 18. An article comprising a substrate; and a cured product of anepoxy resin composition comprising a curing agent, and an epoxy compoundrepresented by Formula 1, an epoxy compound represented by Formula 2, ora combination thereof, a sealing portion comprising the cured product ofthe epoxy resin composition, a substrate portion comprising the curedproduct of the epoxy resin composition, a reinforcement portioncomprising the cured product of the epoxy resin composition, or anadhesive portion comprising the cured product of the epoxy resincomposition:E1-(M1)_(a1)-(L1)_(b1)-(M2)_(a2)-L2-A1-L3-(M3)_(a3)-(L4)_(b2)-(M4)_(a4)-E2  Formula1E3-(A2)_(c1)-(L5)_(b3)-(M5)_(a5)-L6-(M6)_(a6)-L7-(M7)_(a7)-(L8)_(b4)-(A3)_(c2)-E4  Formula2 wherein, in Formulae 1 and 2, M1, M4, M5, and M7 are eachindependently an arylene group represented by Formulae 3a to 3j, M2, M3,and M6 are each independently a naphthalene group represented byFormulae 3g to 3j,

 wherein, in Formulae 3a to 3j,  R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉,R₁₀, R₁₁, and R₁₂ are each independently a hydrogen, a halogen, ahydroxy group, or a substituted or unsubstituted C1-C10 alkyl group; A1,A2, and A3 are each independently a substituted or unsubstituted C4-C12alkylene group, a substituted or unsubstituted C4-C12 alkenylene group,a substituted or unsubstituted C4-C12 alkynylene group, a substituted orunsubstituted C4-C12 alkadienylene group, or a (poly)oxyalkylene groupcomprising a substituted or unsubstituted C1-C5 alkylene group; L1, L2,L3, L4, L5, L6, L7, and L8 are each independently —C(═O)O— or —OC(═O)—,E1, E2, E3, and E4 are each independently an epoxy-containing group, a1,a4, b1, b2, b3, b4, c1, and c2 are each independently 0 or 1, and a2,a3, a5, a6, and a7 are each independently 1 or
 2. 19. The article ofclaim 18, wherein a thermal conductivity of the cured products of theepoxy resin compositions is about 0.25 Watts per meter-Kelvin or more.20. A method of preparing an epoxy compound, the method comprisingproviding a first composition by contacting a compound represented byFormula 11 with a compound represented by Formula 12; preparing a secondcomposition comprising a compound by Formula 1 from the firstcomposition; and recovering the second composition, wherein therecovering of the second composition is performed while the providing ofthe first composition is being performed:E1-(M1)_(a1)-(L1)_(b1)-(M2)_(a2)-L2-A1-L3-(M3)_(a3)-(L4)_(b2)-(M4)_(a4)-E2  Formula1R_(c)-(M1)_(a1)-(L1)_(b1)-(M2)_(a2)-L2-A1-L3-(M3)_(a3)-(L4)_(b2)-(M4)_(a4)-R_(d)  Formula11E-R_(e)  Formula 12 wherein, in Formulae 1, 11, and 12, M1 and M4 areeach independently an arylene group represented by Formulae 3a to 3j, M2and M3 are each independently a naphthalene group represented byFormulae 3g to 3j,

 wherein, in Formulae 3a to 3j,  R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉,R₁₀, R₁₁, and R₁₂ are each independently a hydrogen, a halogen, ahydroxy group, or a substituted or unsubstituted C1-C10 alkyl group, R_(c) and R_(d) are each independently a hydroxy group,  R_(e) is ahalogen; A1 is a substituted or unsubstituted C4-C12 alkylene group, asubstituted or unsubstituted C4-C12 alkenylene group, a substituted orunsubstituted C4-C12 alkynylene group, a substituted or unsubstitutedC4-C12 alkadienylene group, or a (poly)oxyalkylene group containing asubstituted or unsubstituted C1-C5 alkylene group; L1, L2, L3, and L4are each independently —C(═O)O— or —OC(═O)—, E1, E2, and E are eachindependently an epoxy-containing group, a1, a4, b1, and b2 are eachindependently 0 or 1, and a2 and a3 are each independently 1 or
 2. 21.The method of claim 20, wherein the preparing of the second compositionis performed free of a metal catalyst, at a temperature of about 80° C.or more and a pressure of about 1 atmosphere or more.
 22. The method ofclaim 20, further comprising preparing the compound represented byFormula 11 by contacting a compound represented by Formula 13 with anorganic base, before the providing of the first composition:R_(f)-(M1)_(a1)-(L1)_(b1)-(M2)_(a2)-L2-A1-L3-(M3)_(a3)-(L4)_(b2)-(M4)_(a4)-R_(g)  Formula13 wherein, in Formula 13, M1 and M4 are each independently an arylenegroup represented by Formula 3a to 3j, M2 and M3 are each independentlya naphthalene group represented by Formula 3g to 3j, A1 is a substitutedor unsubstituted C4-C12 alkylene group, a substituted or unsubstitutedC4-C12 alkenylene group, a substituted or unsubstituted C4-C12alkynylene group, a substituted or unsubstituted C4-C12 alkadienylenegroup, or a (poly)oxyalkylene group containing a substituted orunsubstituted C1-C5 alkylene group; L1, L2, L3, and L4 are eachindependently —C(═O)O— or —OC(═O)—, a1, a4, b1, and b2 are eachindependently 0 or 1, a2 and a3 are each independently 1 or 2, and R_(f)and R_(g) are each independently R_(h)C(═O)O—, wherein R_(h) is an alkylgroup of 1 to 5 carbon atoms.
 23. The method of claim 22, furthercomprising preparing the compound represented by Formula 13 bycontacting a compound represented by Formula 14 with a compoundrepresented by Formula 15, before the preparing of the compoundrepresented by Formula 11:R_(i)-(M8)_(a8)-(L9)_(b5)-(M9)_(a9)-R_(j)  Formula 14R_(k)-A1-R_(l)  Formula 15 wherein, in Formulae 14 and 15, M8 is anarylene group represented by Formulae 3a to 3j, M9 is a naphthalenegroup represented by Formulae 3g to 3j, A1 is a substituted orunsubstituted C4-C12 alkylene group, a substituted or unsubstitutedC4-C12 alkenylene group, a substituted or unsubstituted C4-C12alkynylene group, a substituted or unsubstituted C4-C12 alkadienylenegroup, or a (poly)oxyalkylene group containing a substituted orunsubstituted C1-C5 alkylene group; L9 is —C(═O)O— or —OC(═O)—, a8 andb5 are each independently 0 or 1, a9 is 1 or 2, R_(i) is R_(m)C(═O)O—,wherein R_(m) is an alkyl group of 1 to 5 carbon atoms, and R_(j),R_(k), and R_(l) are each independently a hydroxy group or a carboxylgroup.